WO2022225017A1

WO2022225017A1 - Solventless composition

Info

Publication number: WO2022225017A1
Application number: PCT/JP2022/018436
Authority: WO
Inventors: 直樹中家; 智規古川; 智恵田中; 勇樹渡辺
Original assignee: 日産化学株式会社
Priority date: 2021-04-23
Filing date: 2022-04-21
Publication date: 2022-10-27
Also published as: TW202311330A; KR20230174249A; CN117321141A; JPWO2022225017A1

Abstract

The present invention provides a solventless composition characterized by comprising: a triazine-ring-containing polymer having a repeating unit structure represented by formula (1), having at least one triazine ring terminal, at least a part of the triazine ring terminal being capped by an amino group having a crosslinking group; a crosslinking agent; and inorganic particles, said solventless composition containing no organic solvent. (In the formula, R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Q represents a C3-C30 bivalent group having a ring structure. The symbol * represents a bond.)

Description

solvent-free composition

The present invention relates to solventless compositions.

In recent years, liquid crystal displays, organic electroluminescence (EL) elements (organic EL displays and organic EL lighting), touch panels, optical semiconductors (light-emitting diodes (LEDs), etc.) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells , and organic thin film transistors (TFTs), demand for highly functional polymer materials has increased.
Specific properties required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, and 7) high film hardness. etc.
In view of this point, the present applicant has found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, high solubility, It has already been found that it can achieve low volume shrinkage and is suitable as a film-forming composition for producing electronic devices (Patent Document 1).

By the way, in the flattening layer and the light scattering layer in the organic EL lighting, it is common to use a composition in which a high refractive index material is dissolved in an organic solvent, and to prepare a thin film by a coating method. In some cases, it was not possible to use a highly polar solvent depending on the type of the solvent.
In view of this point, the present applicant has found that a solventless photocurable adhesive composition containing a triazine ring-containing polymer is suitable as a refractive index adjusting material (Patent Document 2).
However, there is room for improvement in terms of solvent resistance.

WO2010/128661 WO2016/194920

The present invention has been made in view of the above circumstances, has a high refractive index, while maintaining a high solvent resistance even if the film thickness is thick, a cured film that can maintain a high transmittance and a low HAZE It is an object of the present invention to provide a solventless composition capable of forming and further reducing viscosity.

As a result of intensive studies to achieve the above object, the present inventors have found that a triazine having at least one triazine ring terminal and at least part of the triazine ring terminal being blocked with an amino group having a cross-linking group By using a ring-containing polymer, a cross-linking agent, and inorganic fine particles in a solventless composition, it has a high refractive index and maintains high solvent resistance even when the film is thick, while achieving high transmittance and low HAZE. It has been found that a cured film that can be maintained can be formed, and by adding inorganic fine particles to a solvent-free composition containing a triazine ring-containing polymer, the viscosity can be reduced while maintaining a high refractive index. and completed the present invention.

That is, the present invention provides the following solventless composition.
[1] containing a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least part of the triazine ring terminal being blocked with an amino group having a cross-linking group; a triazine ring-containing polymer;
a cross-linking agent;
inorganic fine particles;
including
does not contain organic solvents,
A solvent-free composition characterized by:

(In formula (1), R and R′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q is a ring structure having 3 to 30 carbon atoms; represents a valence group.* represents a bond.)
[2] The inorganic material according to [1], wherein Q in formula (1) represents at least one selected from the group represented by formulas (2) to (13) and formulas (102) to (115). Solvent-based composition.

[In the formulas (2) to (13), R ¹ to R ⁹² are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, represents a halogenated alkyl group or an alkoxy group having 1 to 10 carbon atoms,
R ⁹³ and R ⁹⁴ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
W ¹ and W ² are each independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom, a C 1-10 alkyl group (provided that these may form a ring), or represents a halogenated alkyl group having 1 to 10 carbon atoms.), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.),
X ¹ and X ² are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or formula (14)

(In formula (14), R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. , or represents an alkoxy group having 1 to 10 carbon atoms,
Y ¹ and Y ² independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. ) represents a group represented by
* represents a bond. ]

(In formulas (102) to (115), R ¹ and R ² each independently represent an alkylene group having 1 to 5 carbon atoms which may have a branched structure. * represents a bond. .)
[3] R ¹ to R ⁹² and R ⁹⁸ to R ¹⁰¹ in formulas (2) to (13) are each independently a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 10 carbon atoms; The solventless composition according to [1] or [2].
[4] The solventless composition according to any one of [1] to [3], wherein the arylamino group having a cross-linking group is represented by formula (15).

(In formula (15), R ¹⁰² represents a cross-linking group. * represents a bond.)
[5] The solvent-free composition according to [4], wherein the amino group having the crosslinking group is represented by formula (16).

(In formula (16), R ¹⁰² has the same meaning as above. * represents a bond.)
[6] The solvent-free composition according to [4] or [5], wherein R ¹⁰² is a hydroxy-containing group or (meth)acryloyl-containing group.
[7] The solvent-free composition according to [6], wherein R ¹⁰² is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (i).

(In formula (i), A ¹ represents an alkylene group having 1 to 10 carbon atoms, and A ² is a single bond or the following formula (j)

A3 represents an (a+1) ^-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group ^, A4 represents a hydrogen atom or a methyl group, a represents 1 or 2 and * represents a bond. )
[8] wherein R ¹⁰² is a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and formulas (i-2) to (i-5) below; The solvent-free composition according to [7], which is a group selected from the groups represented by:

(In formulas (i-2) to (i-5), * represents a bond.)
[9] Any of [2] to [8], wherein at least one aromatic ring in Q in the formula (1) contains at least one halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms 2. The solvent-free composition according to 1.
[10] The solvent-free composition according to any one of [1] to [9], wherein a portion of the triazine ring terminal is further capped with an unsubstituted arylamino group.
[11] The solvent-free composition according to any one of [1] to [10], wherein the unsubstituted arylamino group is represented by formula (33).

(In formula (33), * represents a bond.)
[12] The solvent-free composition according to any one of [1] to [11], wherein Q in formula (1) is represented by formula (17).

(In formula (17), * represents a bond.)
[13] The solvent-free composition according to any one of [1] to [12], wherein Q in formula (1) is represented by formula (20).

(In formula (20), * represents a bond.)
[14] The solventless composition according to any one of [1] to [13], wherein the cross-linking agent is a polyfunctional (meth)acrylic compound.
[15] The solvent-free composition according to any one of [1] to [14], wherein the inorganic fine particles contain a metal oxide, metal sulfur or metal nitride.
[16] The solventless composition according to any one of [1] to [15], further comprising a reactive diluent.
[17] The solvent-free composition according to [16], wherein the reactive diluent is a compound having one radically polymerizable group.
[18] The solventless composition according to any one of [1] to [17], which is photocurable.
[19] A film obtained from the solventless composition according to any one of [1] to [18].
[20] An electronic device comprising a substrate and the film according to [19] formed on the substrate.
[21] An optical member comprising a substrate and the film according to [19] formed on the substrate.

According to the present invention, it is possible to form a cured film having a high refractive index and maintaining high solvent resistance even when the film thickness is thick, while maintaining high transmittance and low HAZE, and further lowering the viscosity. A solvent-free composition can be provided.
Films produced from the solvent-free composition of the present invention can exhibit properties such as high heat resistance, high refractive index, low volume shrinkage, and solvent resistance (crack resistance). Organic EL displays and organic EL lighting), touch panels, optical semiconductor devices, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors, lenses, prisms, cameras, binoculars, microscopes, semiconductor exposure equipment, etc. It can be suitably used in the fields of electronic devices and optical materials, such as a member of the case.
In particular, the film produced from the solvent-free composition of the present invention has high transparency and high refractive index and solvent resistance (crack resistance). By using it as a material, its light extraction efficiency (light diffusion efficiency) can be improved, and its durability can be improved.

1 is a ¹ H-NMR spectrum diagram of compound P-1 (polymer compound [5]) obtained in Synthesis Example 1. FIG. 1 is a ¹ H-NMR spectrum diagram of compound P-2 (polymer compound [7]) obtained in Synthesis Example 3. FIG. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-1-1 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-1-2 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-1-3 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-2-1 after exposure to a solvent. 2 is an optical microscope photograph of the surface of the cured film obtained in Example 3-2-2 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-2-3 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-3-1 after exposure to a solvent. 2 is an optical microscope photograph of the surface of the cured film obtained in Example 3-3-2 after being exposed to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-3-3 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-4-1 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-4-2 after exposure to a solvent. 2 is an optical microscope photograph of the surface of the cured film obtained in Example 3-4-3 after being exposed to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-5-1 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-5-2 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-5-3 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-6-1 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-6-2 after exposure to a solvent. 1 is an optical microscope photograph of the surface of a cured film obtained in Example 3-6-3 after exposure to a solvent.

The present invention will be described in more detail below.
A solventless composition according to the present invention comprises a triazine ring-containing polymer, a cross-linking agent, and inorganic fine particles. A solventless composition does not contain an organic solvent.
Here, "free of organic solvent" means substantially free of organic solvent, and specifically indicates that the content of organic solvent is 10% by mass or less.

(1). Triazine Ring-Containing Polymer The triazine ring-containing polymer contains a repeating unit structure represented by the following formula (1).
A triazine ring-containing polymer is, for example, a so-called hyperbranched polymer. A hyperbranched polymer is a highly branched polymer having an irregularly branched structure. The term "irregular" as used herein means that the branch structure is more irregular than that of a dendrimer, which is a highly branched polymer having a regular branch structure.
For example, a triazine ring-containing polymer, which is a hyperbranched polymer, has a structure larger than the repeating unit structure represented by formula (1), and each of the three bonds of the repeating unit structure represented by formula (1) has , and a structure (structure X) in which repeating unit structures represented by formula (1) are bonded. In the triazine ring-containing polymer, which is a hyperbranched polymer, structure X is distributed throughout the triazine ring-containing polymer except for the terminals.
In the triazine ring-containing polymer, which is a hyperbranched polymer, the repeating unit structure may consist essentially of the repeating unit structure represented by formula (1).

* represents a bond.

<<R and R'>>
In the above formula, R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. preferable.
In the present invention, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20. Considering that the heat resistance of the polymer is further improved, the number of carbon atoms in the alkyl group is 1 to 10. More preferably, 1 to 3 are even more preferable. Moreover, the structure of the alkyl group is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

Specific examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl. , n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl -n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl -n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl -n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1 -ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2 ,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2 ,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl Examples include propyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl groups and the like.

Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably 1 to 20, and in consideration of further increasing the heat resistance of the polymer, the number of carbon atoms in the alkoxy group is more preferably 1 to 10. 1 to 3 are even more preferred. The structure of the alkyl moiety is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n -butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n- propoxy, 1-ethyl-2-methyl-n-propoxy group and the like.

Although the number of carbon atoms in the aryl group is not particularly limited, it is preferably 6 to 40. In consideration of further increasing the heat resistance of the polymer, the number of carbon atoms in the aryl group is more preferably 6 to 16. 6 to 13 are even more preferred.
In the present invention, the aryl group includes an aryl group having a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, and cyano groups.
Specific examples of aryl groups include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -phenanthryl, 9-phenanthryl groups and the like.

Although the number of carbon atoms in the aralkyl group is not particularly limited, it is preferably 7 to 20 carbon atoms, and the structure of the alkyl moiety is not particularly limited. Any combination of
In the present invention, the aralkyl group includes an aralkyl group having a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, and cyano groups.
Specific examples include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.

<<Q>>
Q in formula (1) is not particularly limited as long as it is a divalent group having 3 to 30 carbon atoms and having a ring structure.
The ring structure may be an aromatic ring structure or an alicyclic structure.

The above Q preferably represents at least one selected from the group represented by formulas (2) to (13).

* represents a bond.

R ¹ to R ⁹² above each independently represent a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogen atom having 1 to 10 carbon atoms. representing 10 alkoxy groups,
R ⁹³ and R ⁹⁴ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
W ¹ and W ² are each independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom, a C 1-10 alkyl group (provided that these may form a ring), or represents a halogenated alkyl group having 1 to 10 carbon atoms.), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group).
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group and alkoxy group are the same as those described above.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
As the alkyl group and the alkoxy group, the same groups as the alkyl group and the alkoxy group in R and R' can be mentioned.

The halogenated alkyl group having 1 to 10 carbon atoms is obtained by substituting at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms with a halogen atom, and specific examples thereof include trifluoromethyl , 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl , 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2 , 3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4 , 4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3, 4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and perfluorohexyl groups. In the present invention, a perfluoroalkyl group having 1 to 10 carbon atoms is preferred, particularly 1 to 5 carbon atoms, in consideration of enhancing the solubility of the triazine ring-containing polymer in low-polar solvents while maintaining the refractive index. is more preferred, and a trifluoromethyl group is even more preferred.

X ¹ and X ² each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14).
The structures of these alkyl groups, halogenated alkyl groups, alkoxy groups, and alkylene groups are not particularly limited, and may be, for example, linear, branched, cyclic, or combinations of two or more thereof.

* represents a bond.

R ⁹⁸ to R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a representing 10 alkoxy groups,
Y ¹ and Y ² independently represent a single bond or an alkylene group having 1 to 10 carbon atoms.
These halogen atoms, alkyl groups, halogenated alkyl groups and alkoxy groups include the same halogen atoms, alkyl groups, halogenated alkyl groups and alkoxy groups for R ¹ to R ⁹² .

Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene and pentamethylene groups.
The structure of the alkylene group is not particularly limited, and may be linear, branched, cyclic, or a combination of two or more thereof.

Among these, R ¹ to R ⁹² and R ⁹⁸ to R ¹⁰¹ are a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a An alkoxy group of 1 to 5 is preferred, and a hydrogen atom is more preferred.

In the triazine ring-containing polymer of the present invention, when Q contains an aromatic ring, at least one of the aromatic rings contained in Q has a halogen atom or a halogen atom having 1 to 10 carbon atoms. It preferably contains at least one alkyl group. It is generally known that introduction of a fluorine atom into a compound tends to lower its refractive index. Regardless, the refractive index remains above 1.7. The number of halogen atoms or halogenated alkyl groups in the aromatic ring can be any number that can be substituted on the aromatic ring, but considering the balance between maintaining the refractive index and solubility in a solvent, 1 to 4 are preferred, 1 to 2 are more preferred, and 1 is even more preferred. When the aromatic ring is a condensed aromatic ring such as a naphthalene ring, it may have at least one of the above groups as a whole.
Further, when Q contains a plurality of aromatic rings, at least one halogen atom or halogenated alkyl group may be contained in at least one aromatic ring, but all the aromatic rings are halogen atoms or halogen preferably contain at least one halogenated alkyl group, and more preferably all aromatic rings contain one halogen atom or halogenated alkyl group.

In particular, Q is preferably at least one represented by formulas (2) and (5) to (13), and formulas (2), (5), (7), (8), (11) to (13) ) is more preferred. Specific examples of the divalent groups represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulas.

"Ph" represents a phenyl group. * represents a bond.

(Wherein, A is each independently a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms, p is each independently an integer of 0 to 4, q is each independently an integer of 0 to 3, r is an integer of 0 to 2 independently of each other, s is an integer of 0 to 5 independently of each other, t is an integer of 1 to 6, u is an integer of 1 to 4 However, in each group, the sum of p, q, r, and s is 1 or more, "Ph" represents a phenyl group, and * represents a bond.)

Among these, Q is more preferably a divalent group represented by the following formula, since a polymer with a higher refractive index can be obtained.

"Ph" represents a phenyl group. * represents a bond.

(Wherein, A, p, q, r and u represent the same meanings as above. "Ph" represents a phenyl group. * represents a bond.)

In particular, in consideration of further increasing the solubility of the triazine ring-containing polymer in organic solvents such as low-polar solvents, Q is preferably an m-phenylene group represented by formula (17).

(In the formula, * represents a bond.)

In particular, in consideration of further increasing the refractive index of the triazine ring-containing polymer, Q is preferably a group having a diphenyl ether skeleton represented by formulas (18) to (20).

(In the formula, A and p have the same meaning as above. * represents a bond.)

(In the formula, A and p have the same meaning as above. * represents a bond.)

(In the formula, * represents a bond.)

Q in formula (1) represents at least one selected from the group represented by formulas (102) to (115), for example.

* represents a bond.

In formulas (102) to (115), R ¹ and R ² above independently represent an optionally branched alkylene group having 1 to 5 carbon atoms.
Examples of such alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups. is preferred, and an alkylene group having 1 to 2 carbon atoms, more preferably a methylene or ethylene group, most preferably a methylene group.

<Amino group having a cross-linking group>
Moreover, the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and at least part of this triazine ring terminal is blocked with an amino group having a cross-linking group.
The triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and the triazine ring at this terminal usually has two halogen atoms that can be substituted with the amino group having the above-mentioned bridging group. there is Therefore, the amino group having the bridging group may be bonded to the same triazine ring terminal, and when there are a plurality of triazine ring terminals, each may be bonded to a different triazine ring terminal.

The number of cross-linking groups in the amino group having a cross-linking group is not particularly limited, and can be any number. 4 is preferred, 1-2 is more preferred, and 1 is even more preferred.
When the amino group having a cross-linking group has a plurality of cross-linking groups, the plurality of cross-linking groups may have the same structure or different structures.

An amino group having a cross-linking group is represented, for example, by the following formula (X).

(In the formula, Z represents a group having a cross-linking group. * represents a bond.)

In formula (X), Z may be the bridging group itself.
Preferably, the bridging group is attached to the amino group through an arylene group.

The amino group having a cross-linking group is more preferably represented by the following formula (15), particularly preferably represented by the following formula (16).

(In the formula, R ¹⁰² represents a cross-linking group. * represents a bond.)

(In the formula, R ¹⁰² has the same meaning as above. * represents a bond.)

Examples of cross-linking groups include hydroxyl-containing groups, vinyl-containing groups, epoxy-containing groups, oxetane-containing groups, carboxy-containing groups, sulfo-containing groups, thiol-containing groups, and (meth)acryloyl-containing groups. Hydroxy-containing groups and (meth)acryloyl-containing groups are preferred in consideration of improving the heat resistance of the coalescence and the solvent resistance (crack resistance) of the resulting film.

The hydroxy-containing group includes a hydroxy group, a hydroxyalkyl group, and the like, preferably a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably a hydroxyalkyl group having 1 to 5 carbon atoms, and a hydroxy group having 1 to 3 carbon atoms. Alkyl groups are even more preferred.
Hydroxyalkyl groups having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3- Hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy 1-Hydroxyethyl, 1-Hydroxypropyl, 2-Hydroxypropyl, 1-Hydroxybutyl, 2-Hydroxybutyl, 1 -Hydroxy groups such as hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl groups Included are those in which the carbon atom to which the group is attached is a secondary or tertiary carbon atom.

In particular, in consideration of improving heat resistance and high-temperature and high-humidity resistance, it is preferable that the carbon atom to which the hydroxy group is bonded is a primary carbon atom. A hydroxyalkyl group having 1 to 3 carbon atoms is more preferred, a hydroxymethyl group and a 2-hydroxyethyl group are more preferred, and a 2-hydroxyethyl group is most preferred.

Examples of the (meth)acryloyl-containing group include (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, groups represented by the following formula (i), and the like, having an alkylene group having 1 to 10 carbon atoms ( A meth)acryloyloxyalkyl group and a group represented by the following formula (i) are preferred, and a group represented by the following formula (i) is more preferred.

(Wherein, A ¹ represents an alkylene group having 1 to 10 carbon atoms, A ² is a single bond or the following formula (j)

A3 represents an (a+1) ^-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group ^, A4 represents a hydrogen atom or a methyl group, a represents 1 or 2 and * represents a bond. )

Examples of the alkylene group contained in the (meth)acryloyloxyalkyl group having an alkylene group (alkanediyl group) having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propane-1,2-diyl, tetramethylene and butane-1. ,3-diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decamethylene groups. Among these, those having an alkylene group having 1 to 5 carbon atoms are preferable, those having an alkylene group having 1 to 3 carbon atoms are preferable, and 1 carbon atom, in consideration of improving heat resistance and high temperature and high humidity resistance. or 2 alkylene groups are more preferred.

Specific examples of the (meth)acryloyloxyalkyl group include, for example, (meth)acryloyloxymethyl group, 2-(meth)acryloyloxyethyl group, 3-(meth)acryloyloxypropyl group, 4-(meth)acryloyl An oxybutyl group is mentioned.

In formula (i), A ¹ is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group and an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same alkylene groups included in the above (meth)acryloyloxyalkyl group.

^A2 represents a single bond or a group represented by formula (j), preferably a group represented by formula (j).

A ³ is an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and specific examples thereof include an alkylene group having 1 to 5 carbon atoms and the following formula (k-1) ~ (k - 3)

(In the formula, * is the same as above.)
An alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred, and a methylene group and an ethylene group are even more preferred. Examples of the alkylene group for A ³ include alkylene groups having 1 to 5 carbon atoms among the alkylene groups exemplified for A ¹ .

a represents 1 or 2, but 1 is preferred.

Suitable embodiments of the group represented by formula (i) include those represented by the following formula (i-1).

(In the formula, A ¹ , A ³ , A ⁴ and * are the same as above.)

More preferred embodiments of the group represented by formula (i) include those represented by formulas (i-2) to (i-5) below.

(In the formula, * is the same as above.)

Examples of vinyl-containing groups include alkenyl groups with 2 to 10 carbon atoms having a vinyl group at the end. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl groups and the like.

Epoxy-containing groups include epoxy, glycidyl, and glycidyloxy groups. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl and 4-glycidylbutyl groups.

Oxetane-containing groups include oxetan-3-yl, (oxetan-3-yl)methyl, 2-(oxetan-3-yl)ethyl, 3-(oxetan-3-yl)propyl, 4-(oxetan-3- yl) butyl group and the like.

Examples of carboxy-containing groups include carboxy groups and carboxyalkyl groups having 2 to 10 carbon atoms. As the carboxyalkyl group having 2 to 10 carbon atoms, the carbon atom to which the carboxy group is bonded is preferably a secondary carbon atom, and specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and 4- A carboxybutyl group and the like can be mentioned.

The sulfo-containing group includes a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As the sulfoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples are sulfomethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl groups. etc.

Examples of thiol-containing groups include thiol groups and mercaptoalkyl groups having 1 to 10 carbon atoms. The mercaptoalkyl group having 1 to 10 carbon atoms is preferably one in which the carbon atom to which the thiol group is bonded is a primary carbon atom, and specific examples are mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl and 4- A mercaptobutyl group and the like can be mentioned.

Specific examples of amino groups having a cross-linking group include those represented by the following formulas, but are not limited to these.

In the formula, * represents a bond.

An arylamino group having a hydroxyalkyl group can be introduced using a corresponding hydroxyalkyl group-substituted arylamino compound in the production method described below.
Specific examples of hydroxyalkyl group-substituted arylamino compounds include (4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

An arylamino group having a (meth)acryloyloxyalkyl group can be obtained by a method using a corresponding (meth)acryloyloxyalkyl group-substituted arylamino compound, or after introducing an arylamino group having a hydroxyalkyl group into a triazine ring-containing polymer. Furthermore, it can be introduced by a method of reacting a (meth)acrylic acid halide or glycidyl (meth)acrylate on the hydroxy group contained in the hydroxyalkyl group.

An arylamino group having a group represented by formula (i) can be obtained by a method using an arylamino compound having a desired cross-linking group, or by introducing an arylamino group having a hydroxyalkyl group into a triazine ring-containing polymer, followed by Furthermore, it can be introduced by a method of reacting a (meth)acrylic acid ester compound having an isocyanate group represented by the following formula (i') against the hydroxy group contained in the hydroxyalkyl group.

(In the formula, A ³ , A ⁴ and a are the same as above.)

Specific examples of the (meth)acryloyloxyalkyl group-substituted arylamino compound include, for example, those obtained by reacting the hydroxy group of the above hydroxyalkyl group-substituted arylamino compound with (meth)acrylic acid halide or glycidyl (meth)acrylate. Ester compounds such as
Examples of the (meth)acrylic acid halide include (meth)acrylic acid chloride, (meth)acrylic acid bromide and (meth)acrylic acid iodide.
Specific examples of the (meth)acrylic acid ester compound having an isocyanate group represented by the above formula (i′) include, for example, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate and 1,1-(bis Acryloyloxymethyl)ethyl isocyanate may be mentioned. In the present invention, 2-isocyanatoethyl acrylate is preferred from the viewpoint of a simple synthesis method.

In the present invention, particularly suitable triazine ring-containing polymers include those containing repeating units represented by formulas (21) to (28).

(In the formula, R, R', R ¹ to R ⁴ and R ¹⁰² have the same meanings as above.)

(In the formula, R ¹ to R ⁴ and R ¹⁰² have the same meanings as above.)

(In the formula, R ¹⁰² has the same meaning as above.)

(In the formula, R ¹⁰² has the same meaning as above.)

(Wherein, R, R′, R ¹⁶ to R ²³ and R ¹⁰² have the same meanings as above.)

(In the formula, R ¹⁶ to R ²³ and R ¹⁰² have the same meanings as above.)

(In the formula, R ¹⁰² has the same meaning as above.)

(In the formula, R ¹⁰² has the same meaning as above.)

The weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, to further improve heat resistance and reduce shrinkage. From the point of view, 2,000 or more is preferable, and from the viewpoint of further increasing the solubility and reducing the viscosity of the obtained composition, it is preferably 50,000 or less, more preferably 30,000 or less, and 25,000 or less. is more preferred, and 10,000 or less is most preferred.
The weight average molecular weight in the present invention is the average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (hereinafter referred to as GPC) analysis.

The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010/128661 mentioned above.
That is, after reacting a trihalogenated triazine compound and an aryldiamino compound in an organic solvent, for example, an amino compound having a hydroxyalkyl group (hydroxy-containing group), an acryloyloxyalkyl group (acryloyl containing group) and at least one amino compound selected from amino compounds having a group represented by formula (i) (acryloyl-containing group) to obtain the triazine ring-containing polymer of the present invention. be able to.

For example, as shown in Scheme 1 below, a triazine ring-containing polymer (23) is obtained by reacting a triazine compound (29) and an aryldiamino compound (30) in a suitable organic solvent, followed by a terminal blocking agent. It can be obtained by reacting with at least one arylamino compound (31) selected from an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by formula (i).

(Wherein, X independently represents a halogen atom, and R ^a represents a hydroxyalkyl group or a group represented by formula (i).)

Alternatively, for example, as shown in Scheme 2 below, a triazine ring-containing polymer (27) is obtained by reacting a triazine compound (29) and an aryldiamino compound (32) in a suitable organic solvent, followed by end-capping. It can be obtained by reacting with at least one arylamino compound (31) selected from an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by formula (i).

In Scheme 1 or Scheme 2 above, the charging ratio of the aryldiamino compound (30) or (32) is arbitrary as long as the target polymer can be obtained. (30) or (32) is preferably 0.01 to 10 equivalents, more preferably 0.7 to 5 equivalents.
The aryldiamino compound (30) or (32) may be added neat or in the form of a solution dissolved in an organic solvent. Considering ease of operation and ease of reaction control, the latter method is preferred. is preferred.
The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, preferably about -30 to 150°C, more preferably -10 to 100°C.

Another aspect is the method shown in Scheme 3 below. In this method, the triazine ring-containing polymer (23) is obtained by reacting the triazine compound (29) and the aryldiamino compound (30) in a suitable organic solvent, and then obtaining an aryl having a hydroxyalkyl group as a terminal blocking agent. A triazine ring-containing polymer (23′) is obtained by reacting with an amino compound (31′) (first step), and then a hydroxy alkyl group contained in the triazine ring-containing polymer (23′) is It can be obtained by reacting a (meth)acrylic acid ester compound having an isocyanate group represented by formula (i') on the group (second stage).
When the target product is the triazine ring-containing polymer (23'), the reaction in the second step may be omitted and the first step may be completed.

(In the formula, R ^a1 represents a hydroxyalkyl group, and X, A ³ , A ⁴ , R ^a and a have the same meanings as above.)

Moreover, as another aspect, the technique shown in the following scheme 4 can be mentioned. In this method, the triazine ring-containing polymer (27) is obtained by reacting the triazine compound (29) and the aryldiamino compound (32) in a suitable organic solvent, followed by an aryl A triazine ring-containing polymer (27′) is obtained by reacting with an amino compound (31′) (first step), and then an alkyl It can be obtained by reacting a (meth)acrylic acid ester compound having an isocyanate group represented by formula (i') on the group (second stage).
When the triazine ring-containing polymer (27') is the target product, the reaction in the second step is not performed and the first step is sufficient.

In Scheme 3 above, the charging ratio and addition method of the aryldiamino compound (30) in the first step, and the reaction temperature in the reaction until the triazine ring-containing polymer (23′) is obtained are the same as those described in Scheme 1. can be the same.
In the second stage, the charging ratio of the (meth)acrylic acid ester compound having an isocyanate group represented by formula (i') to the triazine ring-containing polymer (23') is hydroxyalkyl group and formula (i) It can be arbitrarily set according to the ratio with the group represented by, preferably 0.1 to 10 equivalents, more preferably 0.1 to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. 5 to 5 equivalents, more preferably 0.7 to 3 equivalents, still more preferably 0.9 to 1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the triazine ring-containing polymer (23′) are groups represented by formula (i), the charging ratio is 1 equivalent of the arylamino compound having a hydroxyalkyl group used. For, the (meth) acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0 to 1.5 equivalents.
The reaction temperature in this reaction is the same as the reaction temperature in the reaction for obtaining the triazine ring-containing polymer (23′), but considering that the (meth)acryloyl group should not undergo polymerization during the reaction, it is 30 ~80°C is preferred, 40 to 70°C is more preferred, and 50 to 60°C is even more preferred.

In Scheme 4 above, the charging ratio, addition method, and reaction temperature of the aryldiamino compound (32) can be the same as those described in Scheme 2.
Further, in the second stage, the charging ratio of the (meth)acrylic acid ester compound having an isocyanate group represented by formula (i') to the triazine ring-containing polymer (27') is hydroxyalkyl group and formula (i) It can be arbitrarily set according to the ratio with the group represented by, preferably 0.1 to 10 equivalents, more preferably 0.1 to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. 5 to 5 equivalents, more preferably 0.7 to 3 equivalents, still more preferably 0.9 to 1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the triazine ring-containing polymer (27′) are groups represented by formula (i), the feed ratio is 1 equivalent of the arylamino compound having a hydroxyalkyl group used. For, the (meth) acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0 to 1.05 equivalents.
The reaction temperature in the reaction is the same, but considering that the (meth)acryloyl group does not polymerize during the reaction, it is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., and 50 to 60°C is even more preferred.

In the second step of

schemes

3 and 4,
Polymerization inhibitors include, for example, N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxyamine or salts thereof, benzoquinones, phenolic polymerization inhibitors, phenothiazine and the like. Among these, in terms of excellent polymerization inhibition effect,
Examples of N-nitrosophenylhydroxyamine salts include N-nitrosophenylhydroxyamine ammonium salts and N-nitrosophenylhydroxyamine aluminum salts.
Examples of benzoquinones include p-benzoquinone and 2-methyl-1,4-benzoquinone.
Phenolic polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol and the like.
The amount of the polymerization inhibitor used is not particularly limited, but for example, it is 1 to 200 ppm in mass ratio with respect to the (meth)acrylic acid ester compound having an isocyanate group represented by the formula (i'). or 10 to 100 ppm.
By using a polymerization inhibitor, even if the reaction temperature is raised to about 60 to 80° C., polymerization of the (meth)acryloyl group can be suppressed and the second stage reaction can be carried out.

As the organic solvent, various solvents commonly used in this type of reaction can be used, such as tetrahydrofuran (THF), dioxane, dimethylsulfoxide; methylurea, hexamethylphosphoramide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-methyl-2-piperidone, N, N'-dimethylethylene urea, N,N,N',N'-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N, Amide solvents such as N-dimethylpropionic acid amide, N,N-dimethylisobutyramide, N-methylformamide, N,N'-dimethylpropylene urea, and mixed solvents thereof can be used.
among others N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and mixtures thereof are preferred, and N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are particularly preferred. is.

In addition, in the reaction of the first step in Scheme 1 or Scheme 2 above, various bases that are commonly used during or after polymerization may be added.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxide calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, 2-aminoethanol, ethyldiethanolamine, diethylaminoethanol and the like.
The amount of the base to be added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (29). These bases may be used in the form of an aqueous solution.
Although it is preferable that no raw material components remain in the resulting polymer, some of the raw materials may remain as long as the effects of the present invention are not impaired.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

A known method may be adopted as a terminal capping method using an amino compound having a cross-linking group.
In this case, the amount of the end blocking agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, relative to 1 equivalent of halogen atoms derived from the surplus triazine compound that was not used in the polymerization reaction. Preferably, 0.5 to 2 equivalents is even more preferred.
Examples of the reaction solvent and reaction temperature include the same conditions as described in the first step reaction of Scheme 1 or Scheme 2 above, and the terminal blocking agent is the aryldiamino compound (30) or (32) You can prepare it at the same time.
In addition, an unsubstituted arylamino compound having no cross-linking group may be used, and the terminals may be blocked with two or more groups. Examples of the aryl group of this unsubstituted arylamino compound are the same as those described above.

Specific unsubstituted arylamino groups include, but are not limited to, those represented by the following formula (33).

* represents a bond.

An unsubstituted arylamino group can be introduced using a corresponding unsubstituted arylamino compound.
Aniline etc. are mentioned as a specific example of an unsubstituted arylamino compound.

Further, when introducing an unsubstituted arylamino group, the ratio of the amino compound having a cross-linking group and the unsubstituted arylamino compound should be such that the solubility in organic solvents and the yellowing resistance are exhibited in a well-balanced manner. The unsubstituted arylamino compound is preferably 0.1 to 1.0 mol, more preferably 0.1 to 0.5 mol, even more preferably 0.1 to 0.3 mol, per 1 mol of the amino compound.

In addition to terminal blocking using an amino compound having a cross-linking group, terminal blocking may be performed using an arylamino compound having a specific heteroatom-containing substituent. By endcapping with an arylamino group having a specific heteroatom-containing substituent, the refractive index of the resulting film can be further increased.
Particular heteroatom-containing substituents include cyano groups, alkylamino groups, arylamino groups, nitro groups, alkylmercapto groups, arylmercapto groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups.
Arylamino groups having a specific heteroatom-containing substituent include those represented by the following formula (34).

In the formula, Y is a "specific heteroatom-containing substituent" and is a cyano group, an alkylamino group, an arylamino group, a nitro group, an alkylmercapto group, an arylmercapto group, an alkoxycarbonyl group or an alkoxycarbonyloxy group. show. m represents an integer of 1 to 5; When m is 2 or more, Y may be the same or different. * represents a bond.

Among these, Y is preferably a cyano group or a nitro group. m is preferably 1. When m is 1, Y is preferably substituted at the para- or meta-position.

Further, when introducing an arylamino group having a specific heteroatom-containing substituent, the ratio of the amino compound having a bridging group to the arylamino compound having a specific heteroatom-containing substituent should be From the viewpoint of exhibiting in a well-balanced manner, 0.1 to 1.0 mol of an arylamino compound having a specific heteroatom-containing substituent is preferable with respect to 1 mol of an amino compound having a cross-linking group, and 0.1 to 0.5 mol. is more preferred, and 0.1 to 0.3 mol is even more preferred.

The content of the triazine ring-containing polymer in the solvent-free composition is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 1 to 10% by mass.

(2). Cross-linking agent The cross-linking agent is not particularly limited as long as it is a compound having two or more substituents capable of reacting with the cross-linking group of the triazine ring-containing polymer described above.
Examples of such compounds include melamine-based compounds having cross-linking substituents such as methylol groups and methoxymethyl groups (e.g., phenoplast compounds, aminoplast compounds, etc.), substituted urea-based compounds, cross-linking groups such as epoxy groups and oxetane groups. Compounds containing forming substituents (e.g., polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing blocked isocyanate groups, compounds having acid anhydride groups, compounds having (meth)acrylic groups, and the like. However, from the viewpoint of heat resistance and storage stability, compounds containing an epoxy group, a blocked isocyanate group, or a (meth)acrylic group are preferable. A polyfunctional epoxy compound and/or a polyfunctional (meth)acrylic compound, which gives a composition having a high molecular weight, are preferred.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specific examples thereof include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol diglycidyl. ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'- methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc. mentioned.

In addition, commercially available products include YH-434 and YH434L (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), which are epoxy resins having at least two epoxy groups, and Epolead GT-401, which is an epoxy resin having a cyclohexene oxide structure. , GT-403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Corporation), bisphenol A type epoxy resins, jER1001, 1002, 1003, 1004, 1007 , 1009, 1010, and 828 (manufactured by Mitsubishi Chemical Corporation), jER807 (manufactured by Mitsubishi Chemical Corporation), which is a bisphenol F type epoxy resin, and jER152 and 154, which are phenol novolak type epoxy resins. (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201 and 202 (manufactured by Nippon Kayaku Co., Ltd.), and cresol novolac type epoxy resins, EOCN-102, 103S, 104S, 1020 and 1025. , 1027 (manufactured by Nippon Kayaku Co., Ltd.), jER180S75 (manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy resin, Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177 , CY179 (manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 (manufactured by CIBA-GEIGY AG), Epicron 200, 400 (manufactured by DIC ( Co., Ltd.), jER871, jER872 (manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), aliphatic polyglycidyl ether Denacol EX- 611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX- 321 (manufactured by Nagase ChemteX Corporation) and the like can also be used.

The polyfunctional (meth)acrylic compound is not particularly limited as long as it has two or more (meth)acrylic groups in one molecule.
Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated Trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide polyacrylate, polyglycerin Polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polybasic acid-modified acrylic oligomer, and the like.

Further, the polyfunctional (meth) acrylic compound is available as a commercial product, specific examples thereof include NK Ester A-200, A-400, A-600, A-1000, A- 9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, APG-100, APG-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12 , PEG400DA, THE-330, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-350 (manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA , NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, Same HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Polymer Vanaresin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) and the like.
The polybasic acid-modified acrylic oligomer is also available as a commercial product, and specific examples include Aronix M-510 and 520 (manufactured by Toagosei Co., Ltd.).

The compound having an acid anhydride group is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid. Specific examples thereof include phthalic anhydride and tetrahydrophthalic anhydride. , hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc. Those having one acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- 1-naphthalenesuccinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-dimethyl-1,2, Those having two acid anhydride groups in the molecule such as 3,4-cyclobutanetetracarboxylic dianhydride can be mentioned.

The compound containing a blocked isocyanate group has two or more blocked isocyanate groups in one molecule in which the isocyanate group (--NCO) is blocked with an appropriate protective group, and when exposed to a high temperature during thermosetting, Especially if the protective group (blocking portion) is removed by thermal dissociation and the resulting isocyanate group undergoes a cross-linking reaction with the cross-linking group (e.g., hydroxy-containing group) of the triazine ring-containing polymer of the present invention. Examples include, but are not limited to, compounds having two or more groups represented by the following formulas in one molecule (these groups may be the same or different).

(In the formula, _Rb represents the organic group of the block portion.)

Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.
Examples of compounds having two or more isocyanate groups in one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, and dimers thereof. , trimers, and reaction products thereof with diols, triols, diamines, or triamines.
Examples of blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; phenol, o-nitrophenol , p-chlorophenol, o-, m- or p-cresol, etc.; lactams, such as ε-caprolactam; Pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; Thiols such as dodecanethiol and benzenethiol.

Compounds containing a blocked isocyanate group are also available as commercial products, and specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (manufactured by Asahi Kasei Corporation), Karenz MOI-BM (registered trademark) (manufactured by Showa Denko K.K.), TRIXENE (registered trademark) BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, BI-7992 (manufactured by Baxenden chemicals LTD) and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. , Cymel series such as tetramethoxymethylbenzoguanamine 1123 (manufactured by Nippon Cytec Industries Co., Ltd.), methylated melamine resin Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, the same Melamine compounds such as Nicalac series such as MX-750LM and methylated urea resins such as MX-270, MX-280 and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. , manufactured by Toagosei Co., Ltd.) and the like.

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes a dehydration condensation reaction with the cross-linking group of the triazine ring-containing polymer of the present invention. A cross-linking reaction proceeds.
Examples of phenoplast compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, Bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane , bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene, and the like.
Phenoplast compounds are also commercially available, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, and BI25X-DF. , BI25X-TPA (manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.

Among these, a polyfunctional (meth)acrylic compound is preferable because it can suppress a decrease in refractive index due to incorporation of a cross-linking agent and the curing reaction proceeds rapidly. A polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton described below is more preferable because of its excellent compatibility.
Examples of polyfunctional (meth)acrylic compounds having such a skeleton include NK Ester A-9300 and NK Ester A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

(Wherein, R ¹¹¹ to R ¹¹³ are each independently a monovalent organic group having at least one (meth)acrylic group at the end.)

In addition, from the viewpoint of further improving the curing speed and increasing the solvent resistance, acid resistance, and alkali resistance of the resulting cured film, it is preferably liquid at 25 ° C. and has a viscosity of 5,000 mPa s or less. Is 1 to 3,000 mPa s, more preferably 1 to 1,000 mPa s, still more preferably 1 to 500 mPa s polyfunctional (meth) acrylic compound (hereinafter referred to as a low-viscosity cross-linking agent), alone or It is preferable to use two or more of them in combination or in combination with the above polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton.
Such low-viscosity cross-linking agents are also available as commercial products. -9E (95mPa s, 25°C), A-GLY-20E (200mPa s, 25°C), A-TMPT-3EO (60mPa s, 25°C), A-TMPT-9EO, ATM -4E (150 mPa s, 25 ° C.), ATM-35E (350 mPa s, 25 ° C.) (both manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. The chain length between (meth) acrylic groups is relatively Long crosslinkers are included.

Furthermore, in consideration of improving the alkali resistance of the resulting cured film, NK Ester A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) ) and the above polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton.

In addition, when a film comprising the triazine ring-containing polymer of the present invention is laminated on a protective film such as a PET or polyolefin film and light is irradiated through the protective film, even the film laminated film can be cured satisfactorily without being inhibited by oxygen. You can get sex. In this case, since the protective film needs to be peeled off after curing, it is preferable to use a polybasic acid-modified acrylic oligomer that gives a film with good peelability.

The above-mentioned cross-linking agents may be used alone or in combination of two or more.
The content of the cross-linking agent in the solvent-free composition is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. ~300 parts by mass, more preferably 100 to 150 parts by mass.

(3). Inorganic Fine Particles By adding inorganic fine particles to a solvent-free composition containing a triazine ring-containing polymer, the viscosity can be lowered while maintaining a high refractive index. Since solvent-free compositions do not contain organic solvents, they generally tend to have high viscosity, but the solvent-free composition of the present invention can reduce the viscosity. Therefore, the solvent-free composition of the present invention can be applied by a coating method such as a slit coating method or an inkjet method, which requires a relatively low viscosity.
In addition, even if inorganic fine particles are added to the solvent-free composition containing the triazine ring-containing polymer, the resulting cured film can maintain a low HAZE.

Examples of inorganic fine particles include Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. It contains oxides, sulfides or nitrides of one or more selected metals, and it is particularly preferred to contain these metal oxides. Incidentally, the inorganic fine particles may be used singly or in combination of two or more.
Specific examples of metal oxides include _Al2O3 , ZnO, _TiO2 , ZrO2, _Fe2O3 _, _Sb2O5 , _BeO , _ZnO , _SnO2 , _CeO2 , _SiO2 _, and _WO3 . are mentioned.
It is also effective to use a plurality of metal oxides as a composite oxide. A composite oxide is a mixture of two or more kinds of inorganic oxides in the production stage of fine particles. For example, composite oxides of TiO ₂ and ZrO ₂ , composite oxides of TiO ₂ , ZrO ₂ and SnO ₂ , composite oxides of ZrO ₂ and SnO ₂ and the like can be mentioned.
Further, it may be a compound of the above metals. Examples include ZnSb ₂ O ₆ , BaTiO ₃ , SrTiO ₃ and SrSnO ₃ . These compounds can be used alone or in admixture of two or more, and may also be used in admixture with the above oxides.

The inorganic fine particles may also be, for example, third metal oxide particles (C) obtained by coating the surfaces of the first metal oxide particles (A) with the second metal oxide particles (B).

The first metal oxide particles (A) can be produced by known methods such as ion exchange, deflocculation, hydrolysis, and reaction methods. Examples of the ion exchange method include at least one metal selected from the group consisting of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. and a method of treating an acid salt of the metal with a hydrogen-type ion exchange resin, or a method of treating a basic salt of the metal with a hydroxyl-type anion exchange resin. Examples of deflocculation include washing the gel obtained by neutralizing the acid salt of the metal with a base or neutralizing the basic salt of the metal with an acid, followed by peptization with an acid or a base. method. Examples of the hydrolysis method include a method of hydrolyzing the alkoxide of the above metal, or a method of hydrolyzing the basic salt of the above metal under heating and then removing unnecessary acid. Examples of the reaction method include a method of reacting the metal powder with an acid.

The first metal oxide particles (A) are preferably oxides of metals having a valence of 2 to 6, such as Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta , W, Pb, Bi, Ba, Al, Sr, Hf and Ce. Forms of metal oxides include, for example, _TiO2 , _Fe2O3 , _CuO , ZnO, _Y2O3 , _ZrO2 , _Nb2O5 _, _MoO3 _, _In2O3 _, _SnO2 , _Sb2O5 _. , Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O ₃ , BaO, Al ₂ O ₃ , SrO, HfO ₂ , CeO ₂ and the like. These metal oxides can be used singly or in combination of two or more. Examples of the method of combining the metal oxides include a method of mixing several types of the metal oxides, a method of compounding the metal oxides, and a method of forming a solid solution of the metal oxides at the atomic level.

Combinations of the metal oxides include, for example, SnO ₂ —TiO ₂ composite particles in which SnO ₂ particles and TiO ₂ particles are chemically bonded at their interfaces, and SnO ₂ particles and WO ₃ particles. SnO ₂ —WO ₃ composite particles in which are chemically bonded at their interfaces, and SnO ₂ —ZrO in which SnO ₂ particles and ZrO ₂ particles are chemically bonded at their interfaces. ₂ composite particles, and TiO ₂ --ZrO ₂ --SnO ₂ composite particles obtained by forming a solid solution of TiO ₂ , ZrO ₂ and SnO ₂ at the atomic level.

The _first metal _oxide _particles ₍ _A ) can also be used as a compound by _combining metal components. ZnO, BaTiO ₃ , SrTiO ₃ , aluminum-doped zinc oxide, and the like.

When the first metal oxide particles (A) contain TiO ₂ , the TiO ₂ contained in the particles has any of anatase, rutile, anatase/rutile mixed, and brookite crystal structures. However, among these, those containing the rutile type are preferable in consideration of the refractive index and transparency of the resulting film.

Furthermore, the first metal oxide particles (A) form a thin film layer made of a metal oxide such as zirconium oxide, silicon oxide, and aluminum oxide on the surface from the viewpoint of suppressing the activity (for example, photocatalytic performance). You may The thin film layer can be formed, for example, by adding a zirconium compound to an aqueous dispersion of the first metal oxide particles (A) and heating the mixture at 40 to 200.degree. Examples of the zirconium compound include zirconium oxychloride, zirconium chloride, zirconium hydroxide, zirconium sulfate, zirconium nitrate, zirconium oxynitrate, zirconium acetate, zirconyl carbonate, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium ethylhexanoate, and stearic acid. zirconium, zirconium octylate, zirconium ethoxide, zirconium-n-propoxide, zirconium isopropoxide, zirconium-n-butoxide, zirconium-isopropoxide, zirconium-t-butoxide, zirconium tetraacetylacetonate and the like, Zirconium oxychloride is preferred. The amount of the zirconia compound used, as zirconium oxide, is preferably 3 to 50% by mass relative to the first metal oxide particles (A) used.

The primary particle size of the first metal oxide particles (A) (observed with a transmission electron microscope) is preferably 2 to 60 nm, more preferably 2 to 30 nm, from the viewpoints of dispersion stability, refractive index and transparency of the resulting film. More preferably, 2 to 20 nm is particularly preferred.
The dynamic light scattering particle diameter (according to the dynamic light scattering method), which is the secondary particle diameter of the first metal oxide particles (A), is determined as 5 to 100 nm is preferred, 5 to 50 nm is more preferred, and 5 to 30 nm is particularly preferred.

The first metal oxide particles (A) can be synthesized, for example, according to the method described in International Publication No. 2013/081136.

The second metal oxide particles (B) are preferably oxide particles of at least one metal selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb and W. The second metal oxide particles (B) are in the form of metal oxides, for example, SiO ₂ , Al ₂ O ₃ , SnO ₂ , ZrO ₂ , MoO ₃ , Sb ₂ O ₅ , WO ₃ and the like. can. And these metal oxides can be used individually by 1 type, and can also be used in combination of 2 or more type. Examples of the method of combining the metal oxides include a method of mixing several types of the metal oxides, a method of compounding the metal oxides, and a method of forming a solid solution of the metal oxides at the atomic level.

Specific examples of the second metal oxide particles (B) include, for example, SnO ₂ —WO ₃ composite particles, SnO ₂ particles in which SnO ₂ particles and WO ₃ particles are chemically bonded at their interface to form a composite. SnO ₂ —SiO ₂ composite particles in which particles and SiO ₂ particles are chemically bonded at their interfaces, and SnO ₂ particles, WO ₃ particles and SiO ₂ particles are chemically bonded at their interfaces. SnO ₂ —WO ₃ —SiO ₂ composite particles produced and composited, SnO ₂ —MoO ₃ — composited by chemical bonding of SnO ₂ particles, MoO ₃ particles and SiO ₂ particles at their interfaces Examples include SiO ₂ composite particles, Sb ₂ O ₅ -SiO ₂ composite particles in which Sb ₂ O ₅ particles and SiO ₂ particles are chemically bonded at their interface to form a composite.

When using multiple kinds of metal oxides as the second metal oxide particles (B), the ratio (mass ratio) of the metal oxides contained is not particularly limited, but for example, SnO ₂ —SiO ₂ composite The particles preferably have a SiO ₂ /SnO ₂ mass ratio of 0.1 to 5, and the Sb ₂ O ₅ —SiO ₂ composite particles preferably have a Sb ₂ O ₅ /SiO ₂ mass ratio of 0.1 to 5.

The second metal oxide particles (B) can be produced by known methods such as an ion exchange method and an oxidation method. Examples of the ion exchange method include a method of treating an acid salt of the above metal with a hydrogen ion exchange resin. Examples of the oxidation method include a method of reacting the powder of the metal or the oxide of the metal with hydrogen peroxide.

The primary particle size of the second metal oxide particles (B) (observed with a transmission electron microscope) is preferably 5 nm or less, more preferably 1 to 5 nm, from the viewpoints of dispersion stability and the refractive index and transparency of the resulting film. preferable.

The third metal oxide particles (C) are metal oxide particles obtained by coating the surfaces of the first metal oxide particles (A) with the second metal oxide particles (B). Examples of the manufacturing method include the following first method and second method.

In the first method, an aqueous dispersion containing the first metal oxide particles (A) and an aqueous dispersion containing the second metal oxide particles (B) are separated by (B)/(A). After mixing so that the mass ratio (converted to metal oxide) is 0.05 to 0.5, the aqueous dispersion is heated. For example, an aqueous dispersion containing the first metal oxide particles (A) and Sb ₂ O ₅ —SiO ₂ composite particles (Sb ₂ O ₅ /SiO ₂ =0. 1 to 5) by mixing with the aqueous dispersion containing 1 to 5) so that the above mass ratio is 0.05 to 0.5, and heating the aqueous dispersion obtained by mixing at 70 to 350 ° C. An aqueous dispersion of the third metal oxide particles (C) in which the surfaces of the first metal oxide particles (A) are coated with the Sb ₂ O ₅ —SiO ₂ composite particles is obtained.

In the second method, an aqueous dispersion containing the first metal oxide particles (A), a water-soluble tin oxide alkali salt and a silicon oxide alkali salt as the second metal oxide particles (B), SnO ₂ After mixing so that the mass ratio represented by /SiO ₂ (value in terms of metal oxide) is 0.1 to 5, cation exchange is performed to remove alkali metal ions SnO ₂ —SiO obtained by ₂ and an aqueous dispersion of composite particles so that the mass ratio represented by (B)/(A) (in terms of metal oxide) is 0.05 to 0.5, and then mixed. It is a method of heating an aqueous dispersion. As the aqueous solution of water-soluble alkali salt used in the second method, an aqueous solution of sodium salt can be preferably used. For example, after mixing an aqueous dispersion containing the first metal oxide particles (A) and an aqueous solution of sodium stannate and sodium silicate as the second metal oxide particles (B), cation exchange is performed to obtain and an aqueous dispersion of SnO ₂ —SiO ₂ composite particles obtained above are mixed so that the mass ratio is 0.05 to 0.5, and the aqueous dispersion is heated at 70 to 350° C. to obtain a first An aqueous dispersion of the third metal oxide particles (C) in which the surface of the metal oxide particles (A) as nuclei is coated with the second metal oxide particles (B) composed of SnO ₂ —SiO ₂ composite particles. can get.

The temperature at which the first metal oxide particles (A) and the second metal oxide particles (B) are mixed is usually 1 to 100°C, preferably 20 to 60°C. The heating temperature after mixing is preferably 70 to 350°C, more preferably 70 to 150°C. The heating time after mixing is usually 10 minutes to 5 hours, preferably 30 minutes to 4 hours.

The aqueous dispersion of the third metal oxide particles (C) may contain any component. In particular, by containing oxycarboxylic acids, it is possible to further improve performance such as dispersibility of the third metal oxide particles (C). Examples of the oxycarboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid and glycolic acid. The content of the oxycarboxylic acids is preferably about 30% by mass or less with respect to all metal oxides in the third metal oxide particles (C).

Further, the dispersion of the third metal oxide particles (C) may contain an alkaline component. Examples of the alkali component include alkali metal hydroxides such as Li, Na, K, Rb, and Cs; ammonia; ethylamine, isopropylamine, n-propylamine, n-butylamine, diethylamine, di-n-propylamine, Diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, triamylamine (tri-n-pentylamine), tri-n-hexylamine, tri-n-octylamine , dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, etc. primary, secondary, and tertiary alkylamines; benzylamine, dimethylbenzylamine, etc. aralkylamines; cycloaliphatic amines, such as piperidine; monoethanolamine , alkanolamine such as triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide. These may be used individually by 1 type, or may be used in combination of 2 or more type. The content of the alkali component is preferably about 30% by mass or less with respect to all metal oxides in the third metal oxide particles (C). Moreover, these alkali components can be used in combination with the above oxycarboxylic acid.

When it is desired to further increase the concentration of the aqueous dispersion of the third metal oxide particles (C), it can be concentrated to a maximum of about 65% by mass by a conventional method. The method includes, for example, an evaporation method and an ultrafiltration method. Further, when it is desired to adjust the pH of this aqueous dispersion, the alkali metal hydroxide, amine, quaternary ammonium salt, oxycarboxylic acid, etc. may be added.
The total metal oxide concentration of the solvent dispersion of the third metal oxide particles (C) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.

By replacing the aqueous medium of the aqueous dispersion of the third metal oxide particles (C) with a hydrophilic organic solvent, an organic solvent dispersion of the third metal oxide particles (C) is obtained. This substitution can be carried out by an ordinary method such as a distillation method or an ultrafiltration method. Examples of the hydrophilic organic solvent include lower alcohols such as methanol, ethanol, isopropanol and 1-propanol; ethers such as propylene glycol monomethyl ether; linear amides such as dimethylformamide and N,N-dimethylacetamide; -cyclic amides such as methyl-2-pyrrolidone, glycols such as ethyl cellosolve and ethylene glycol.

The primary particle size of the third metal oxide particles (C) (observed with a transmission electron microscope) is preferably 20 nm or less from the viewpoint of dispersion stability and the refractive index and transparency of the resulting film.
The dynamic light scattering particle diameter (according to the dynamic light scattering method), which is the secondary particle diameter of the third metal oxide particles (C), is determined by 2 to 100 nm is preferred.

Further, the inorganic fine particles used in the present invention may be surface-modified inorganic fine particles. Such inorganic fine particles may have at least one of a hydrophilic group and a crosslinkable group on the surface.
Inorganic fine particles having at least one of a hydrophilic group and a crosslinkable group on the surface (hereinafter sometimes referred to as "surface-modified inorganic fine particles") are, for example, the above inorganic fine particles as core particles, and hydrophilic It is obtained by modifying the surface of the core particles with at least one of an organosilicon compound having a group and an organosilicon compound having a crosslinkable group.
By using surface-modified inorganic fine particles as the inorganic fine particles, the dispersion stability in the resin can be improved, and the HAZE of the cured film can be further suppressed.

Organosilicon compounds have hydrolyzable groups that generate Si—OH groups upon hydrolysis. Hydrolyzable groups include, for example, silicon-bonded alkoxy groups and silicon-bonded acetoxy groups. The number of hydrolyzable groups in the organosilicon compound is not particularly limited, but may be 1 to 3, for example.

Examples of hydrophilic groups include polyether groups such as polyoxyethylene groups, polyoxypropylene groups, and polyoxybutylene groups.

Examples of organosilicon compounds having a hydrophilic group include [methoxy(polyethyleneoxy)n-propyl]trimethoxysilane, [methoxy(polyethyleneoxy)n-propyl]triethoxysilane, [methoxy(polyethyleneoxy)n-propyl ] Tripropoxysilane, [methoxy (polyethyleneoxy) n-propyl] triacetoxysilane, [methoxy (polypropyleneoxy) n-propyl] trimethoxysilane, [methoxy (polypropyleneoxy) n-propyl] triethoxysilane, [methoxy ( polypropyleneoxy)n-propyl]tripropoxysilane, "methoxy(polypropyleneoxy)n-propyl" triacetoxysilane, [methoxy(polybutyleneoxy)n-propyl]trimethoxysilane, [methoxy(polybutyleneoxy)n-propyl ] Tripropoxysilane, [methoxy(polybutyleneoxy)n-propyl]triacetoxysilane, [methoxy(polyethyleneoxy)n-propyl]dimethoxymethylsilane, [methoxy(polyethyleneoxy)n-propyl]diethoxymethylsilane, [ Methoxy(polyethyleneoxy)n-propyl]dipropoxymethylsilane, [methoxy(polyethyleneoxy)n-propyl]diacetoxymethylsilane, [methoxy(polypropyleneoxy)n-propyl]dimethoxymethylsilane, [methoxy(polypropyleneoxy)n -propyl]diethoxymethylsilane, [methoxy(polypropyleneoxy)n-propyl]dipropoxymethylsilane, [methoxy(polypropyleneoxy)n-propyl]diacetoxymethylsilane, [methoxy(polybutyleneoxy)n-propyl]dimethoxy Methylsilane, [methoxy(polybutyleneoxy)n-propyl]diethoxymethylsilane, [methoxy(polybutyleneoxy)n-propyl]dipropoxymethylsilane, [methoxy(polybutyleneoxy)n-propyl]diacetoxymethylsilane etc.

The crosslinkable group is not particularly limited as long as it is a group capable of forming a crosslinked structure by reacting with a crosslinker, and examples thereof include radically polymerizable groups, epoxy groups, and amino groups.
Examples of radically polymerizable groups include allyl groups and (meth)acryloyloxy groups.

Organosilicon compounds having radically polymerizable groups include, for example, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane. , 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 10-methacryloxypropylmethyldimethoxysilane and roxydecyltrimethoxysilane.
Examples of organosilicon compounds having an epoxy group include 3-glycidoxypropyltrimethoxysilane and 8-glycidoxyoctyltrimethoxysilane.
Examples of organosilicon compounds having an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and the like.
These may be used individually by 1 type, or may be used in combination of 2 or more type.

The bonding amount of the organosilicon compound to the surface of the core particles is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, relative to the core particles.

The primary particle size of the inorganic fine particles or surface-modified inorganic fine particles (observed with a transmission electron microscope) is preferably 20 nm or less from the viewpoints of dispersion stability, refractive index and transparency of the resulting film.
The secondary particle diameter (by dynamic light scattering method) of the inorganic fine particles or the surface-modified inorganic fine particles is preferably 2 to 100 nm, more preferably 5 to 50 nm, from the viewpoint of dispersion stability, refractive index and transparency of the obtained film. Preferably, 5 to 20 nm is even more preferred.

For example, the surface-modified inorganic fine particles are prepared by adding a predetermined amount of an organosilicon compound to an aqueous dispersion of core particles or a dispersion in a hydrophilic organic solvent, hydrolyzing the organosilicon compound with a catalyst such as dilute hydrochloric acid, and treating the surface of the core particles. It can be obtained by binding to

The aqueous dispersion or hydrophilic organic solvent dispersion of the core particles can be further replaced with a hydrophobic organic solvent. This replacement method can be carried out by a conventional method such as a distillation method or an ultrafiltration method. Examples of hydrophobic solvents include ketones such as methyl ethyl ketone and methyl isobutyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.

The organic solvent dispersion of the core particles may contain optional components. In particular, by containing phosphoric acid, phosphoric acid derivatives, phosphoric acid-based surfactants, oxycarboxylic acids, etc., the dispersibility of the core particles can be further improved. Examples of phosphoric acid derivatives include phenylphosphonic acid and metal salts thereof. Examples of phosphoric acid-based surfactants include Disperbyk (manufactured by BYK-Chemie), Phosphanol (manufactured by Toho Chemical Industry Co., Ltd.), and Nikkor (manufactured by Nikko Chemicals Co., Ltd.). Oxycarboxylic acids include, for example, lactic acid, tartaric acid, citric acid, gluconic acid, malic acid and glycolic acid. The content of these optional components is preferably about 30% by mass or less with respect to all metal oxides in the core particles.

Considering the dispersion stability, the concentration of the core particles in the organic solvent dispersion is preferably 10 to 60% by mass, more preferably 30 to 50% by mass.

Although the refractive index of the inorganic fine particles is not particularly limited, it is preferably 1.6 to 2.6, more preferably 1.8 to 2.6, from the viewpoint of not lowering the refractive index of the resulting film. The refractive index of the inorganic fine particles is determined, for example, by measuring the refractive index of a liquid of inorganic fine particles dispersed in a solvent or resin having a known refractive index with an Abbe refractometer and extrapolating from the value, or by extrapolating the value. The refractive index of the film or cured product is measured with an Abbe refractometer or spectroscopic ellipsometry, and the refractive index can be extrapolated from the measured value.

The content of the inorganic fine particles in the solvent-free composition may be within a range that does not impair the dispersibility in the final composition obtained. It is possible to control according to gender. For example, it can be added in the range of 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, with respect to 100 parts by mass of the triazine ring-containing polymer. And from the viewpoint of obtaining solvent resistance, it is more preferably 10 to 300 parts by mass.

(4). Reactive Diluent The solventless compositions of the present invention preferably contain a reactive diluent.
The reactive diluent is a low-molecular-weight compound having one reactive group that reacts with at least one of the cross-linking group of the triazine ring-containing polymer and the cross-linking agent. can be used instead of organic solvents.

As such reactive diluents, compounds having one radically polymerizable group and compounds having one cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group are generally used.

The molecular weight of the reactive diluent is not particularly limited, and examples thereof include 200 or less.

As the reactive diluent, a compound having one radically polymerizable group is preferable, and at least one compound represented by the following formulas (A) and (B) is more preferable in terms of excellent solubility of the triazine ring-containing polymer. .

In formula (A), R ²⁰¹ and R ²⁰³ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a polymerizable carbon-carbon double bond-containing group, and R ²⁰² is a hydrogen atom. , or an alkyl group having 1 to 10 carbon atoms. provided that either one of R ²⁰¹ and R ²⁰³ is a polymerizable carbon-carbon double bond-containing group, and both R ²⁰¹ and R ²⁰³ are polymerizable carbon-carbon double bond-containing groups at the same time; no. Also, when R ²⁰¹ is a polymerizable carbon-carbon double bond-containing group, R ²⁰² and R ²⁰³ may together with N form a ring structure.
The structure of the alkyl group is not particularly limited, and may be linear, branched, cyclic, or a combination of two or more thereof.
In formula (B), R ²⁰⁴ represents a hydrogen atom or a methyl group. n represents an integer of 1-2.

Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl- n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n- Examples include propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl groups.
An alkyl group having 1 to 5 carbon atoms is preferred.

The polymerizable carbon-carbon double bond-containing group is not particularly limited, but is a hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms-carbon double bond-containing hydrocarbon group (alkenyl group). are preferred, for example, ethenyl (vinyl), n-1-propenyl, n-2-propenyl (allyl group), 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2- methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-2-pentenyl, n-3- Pentenyl, n-4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2- methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1- dimethyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, n-1-hexenyl, n-2-hexenyl, n-3-hexenyl, Examples include n-4-hexenyl, n-5-hexenyl, n-heptenyl, n-octenyl, n-nonenyl and n-decenyl groups.

Specific examples of the compound represented by formula (A) include N-vinylformamide, N-vinylacetamide, N-allylformamide, N-allylacetamide, 4-acryloylmorpholine, (meth)acrylamide, N-methyl(meth) acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, etc. but N-vinylformamide, 4-acryloylmorpholine, N,N-dimethylacrylamide and N,N-diethyl(meth)acrylamide are preferred.
Specific examples of the compound represented by formula (B) include tetrahydrofuran-2-ylmethyl acrylate, tetrahydrofuran-2-ylmethyl methacrylate, tetrahydrofuran-2-ylethyl acrylate, and tetrahydrofuran-2-ylethyl methacrylate.
The reactive diluents described above may be used alone or in combination of two or more.

The content of the reactive diluent in the solvent-free composition is not particularly limited, and is preferably 1 to 2000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Considering the degree of improvement, solvent resistance and viscosity, it is preferably 500 to 1800 parts by mass, more preferably 1000 to 1500 parts by mass.

The solvent-free composition of the present invention can also contain an initiator suitable for each cross-linking agent and reactive diluent. As described above, when a polyfunctional epoxy compound and/or a polyfunctional (meth)acrylic compound is used as a cross-linking agent, photocuring proceeds to give a cured film without using an initiator. In some cases, an initiator may be used.

When using a polyfunctional epoxy compound as a crosslinking agent, a photoacid generator or a photobase generator can be used.
The photoacid generator may be appropriately selected from known ones and used. For example, onium salt derivatives such as diazonium salts, sulfonium salts and iodonium salts can be used.
Specific examples include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl) diaryliodonium salts such as iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4′-bis(diphenylsulfonio)phenylsulfide-bishexafluoroantimonate, 4,4′-bis(diphenylsulfonate e) phenylsulfide-bishexafluorophosphate, 4,4′-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bishexafluoroantimonate, 4,4′-bis[di(β-hydroxyethoxy) ) phenylsulfonio]phenylsulfide-bis-hexafluorophosphate, 4-[4′-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-[4′-(benzoyl)phenylthio ] and triarylsulfonium salts such as phenyl-bis(4-fluorophenyl)sulfonium hexafluorophosphate.

These onium salts may be commercially available products, and specific examples include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI- L150, SI-L160, SI-L110, SI-L147 (manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (manufactured by Union Carbide company), CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by San-Apro Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-171 (manufactured by San-Apro Co., Ltd.) Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011 , CD-1012 (manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI- 105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB -101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI -022T (manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), and the like.

On the other hand, as the photobase generator, it may be appropriately selected from known ones and used. etc. can be used.
Specific examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2 -nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl- 3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4 - dihydropyridine and the like.
Commercially available photobase generators may also be used, and specific examples thereof include TPS-OH, NBC-101 and ANC-101 (all product names, manufactured by Midori Kagaku Co., Ltd.).

When a photoacid or base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound.
If necessary, an epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.

On the other hand, when using a polyfunctional (meth)acrylic compound, a photoradical polymerization initiator can be used.
As the radical photopolymerization initiator, it may be appropriately selected and used from known ones. is mentioned.
In particular, a photocleavable photoradical polymerization initiator is preferred. The photo-cleavable photoradical polymerization initiator is described in Latest UV Curing Techniques (page 159, published by: Kazuhiro Takasusu, published by: Technical Information Institute, 1991).
Commercially available radical photopolymerization initiators include, for example, BASF trade name: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850 , CG24-61, OXE01, OXE02, Darocure 1116, 1173, MBF, manufactured by BASF Product name: Lucilin TPO, manufactured by UCB Product name: Ebecryl P36, manufactured by Fratetzuri Lamberti Product name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B and the like.
When using a photoradical polymerization initiator, it is preferable to use it in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound, and to use it in the range of 1 to 150 parts by weight. is more preferred.

Furthermore, to the solvent-free composition of the present invention, a polyfunctional thiol compound having two or more mercapto groups in the molecule is added for the purpose of promoting the reaction between the triazine ring-containing polymer and the cross-linking agent. You may
Specifically, a polyfunctional thiol compound represented by the following formula is preferred.

The above L represents a divalent to tetravalent organic group, preferably a divalent to tetravalent aliphatic group having 2 to 12 carbon atoms or a divalent to tetravalent heterocyclic ring-containing group, and a divalent to tetravalent carbon number of 2 An aliphatic group of ~8 or a trivalent group having an isocyanuric acid skeleton (1,3,5-triazine-2,4,6(1H,3H,5H)-trione ring) represented by the following formula is more preferable. .
The above n represents an integer of 2 to 4 corresponding to the valence of L.

(In the formula, "·" indicates a bond with an oxygen atom.)

Specific compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4 , 6-(1H,3H,5H)-trione, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) and the like. be done.
These polyfunctional thiol compounds are also commercially available, and examples thereof include Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (manufactured by Showa Denko KK).
These polyfunctional thiol compounds may be used singly or in combination of two or more.

When using a polyfunctional thiol compound, the amount added is not particularly limited as long as it does not adversely affect the resulting film, but in the present invention, the solid content of 100% by mass, 0.01 to 10 mass % is preferable, and 0.03 to 6% by mass is more preferable.

The solvent-free composition of the present invention may contain other components other than the triazine ring-containing polymer and the cross-linking agent, such as leveling agents, surfactants and silane coupling agents, as long as they do not impair the effects of the present invention. may contain additives.
Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol; Polyoxyethylene alkylallyl ethers such as ethers; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate sorbitan fatty acid esters such as; Nonionic surfactants such as sorbitan fatty acid esters, trade names Ftop EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (former Jemco Co., Ltd.)), trade names Megafac F171, F173, R- 08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.), trade names Fluorine-based surfactants such as Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK -302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BYK-Chemie Japan Co., Ltd.) and the like.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferable.

The solvent-free composition of the present invention can be applied to a substrate and then heated or irradiated with light to form a desired cured film.
Any method can be used for applying the solventless composition, and examples thereof include spin coating, dipping, flow coating, inkjet, jet dispenser, spraying, bar coating, gravure coating, slit coating, and roll coating. method, transfer printing method, brush coating method, blade coating method, air knife coating method and the like can be used.

In addition, as the base material, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, metal nanowires, polyethylene terephthalate (PET), plastic, glass, A base material made of quartz, ceramics, or the like can be mentioned, and a flexible base material having flexibility can also be used.
The calcination temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at, for example, 110 to 400°C.
The baking method is not particularly limited. For example, a hot plate or an oven may be used to evaporate under an appropriate atmosphere such as air, an inert gas such as nitrogen, or vacuum.
The sintering temperature and sintering time may be selected in accordance with the process steps of the intended electronic device, and the sintering conditions may be selected such that the physical properties of the obtained film are suitable for the required characteristics of the electronic device.
The conditions for light irradiation are not particularly limited either, and suitable irradiation energy and time may be adopted according to the triazine ring-containing polymer and cross-linking agent used.

The film and cured film of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage. A component used in manufacturing touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFT), lenses, prism cameras, binoculars, microscopes, semiconductor exposure devices, etc. etc., can be suitably used in the fields of electronic devices and optical materials.
In particular, the film and cured film produced from the solvent-free composition of the present invention have high transparency and a high refractive index, so when used as a planarizing film, a light scattering layer, and a sealing material for organic EL lighting. In addition, the light extraction efficiency (light diffusion efficiency) can be improved, and the durability can be improved.

When the solvent-free composition of the present invention is used for the light scattering layer of organic EL lighting, as the light diffusing agent, a known organic-inorganic composite light diffusing agent, organic light diffusing agent, or inorganic light diffusing agent can be used. , is not particularly limited. These may be used alone, may be used in combination of two or more of the same type, or may be used in combination of two or more of different types.

Examples of the organic-inorganic composite light diffusing agent include melamine resin/silica composite particles.
Examples of organic light diffusing agents include crosslinked polymethylmethacrylate (PMMA) particles, crosslinked polymethylacrylate particles, crosslinked polystyrene particles, crosslinked styrene-acrylic copolymer particles, melamine-formaldehyde particles, silicone resin particles, silica-acrylic composite particles, and nylon particles. , benzoguanamine-formaldehyde particles, benzoguanamine/melamine/formaldehyde particles, fluorine resin particles, epoxy resin particles, polyphenylene sulfide resin particles, polyethersulfone resin particles, polyacrylonitrile particles, polyurethane particles, and the like.
Examples of inorganic light diffusing agents include calcium carbonate (CaCO ₃ ), titanium oxide (TiO ₂ ), barium sulfate (BaSO ₄ ), aluminum hydroxide (Al(OH) ₃ ), silica (SiO ₂ ), talc, and the like. However, titanium oxide (TiO ₂ ) and aggregated silica particles are preferred, and non-aggregated titanium oxide (TiO ₂ ) is more preferred, from the viewpoint of further enhancing the light diffusibility of the resulting cured film.
These light diffusing agents may be used after being surface-treated with an appropriate surface modifier.

The present invention will be described in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples. In addition, each measuring apparatus used in the examples is as follows.

[ ¹ H-NMR]
Apparatus: Bruker NMR System AVANCE III HD 500 (500 MHz)
Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ )
Reference substance: tetramethylsilane (TMS) (δ0.0 ppm)
[GPC]
Apparatus: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000
Column temperature: 40°C
Solvent: dimethylformamide (DMF)
Detector: UV (271 nm)
Calibration curve: standard polystyrene [viscosity]
Apparatus: EMS viscometer EMS-1000 manufactured by Kyoto Electronics Co., Ltd.
[Ellipsometer]
Equipment: JA Woollam Japan multi-incidence angle spectroscopic ellipsometer VASE
[Spectrophotometer]
Equipment: CM-3700A manufactured by Konica Minolta
[Optical microscope]
Apparatus: OLYMPUS BX51 manufactured by Olympus Optical Co., Ltd.
[exposure]
Device: Compact UV LED irradiator NS395-CLT-100W3020 manufactured by Nitride Semiconductor Co., Ltd.

[1] Synthesis of triazine ring-containing polymer [Synthesis Example 1] Synthesis of polymer compound [5]

1,3-phenylenediamine [2] (52.78 g, 0.488 mol, manufactured by Amino-Chem), 2,2'-bis(trifluoromethyl)-4,4'- Diaminodiphenyl ether [3] (82.05 g, 0.244 mol, manufactured by Wuhan Sunshine) and N-methyl-2-pyrrolidone (NMP, 1822.89 g, manufactured by Kanto Chemical Co., Ltd.) were added, and after nitrogen substitution, 1,3-phenylenediamine [2] and 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether [3] were dissolved in NMP with stirring. Then, it is cooled to −5° C. in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (150.00 g, 0.813 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). was added while making sure that the internal temperature did not exceed 5°C, and finally washed away with NMP (227.86 g). After stirring for 30 minutes, the reaction solution was heated until the internal temperature reached 85°C ± 5°C. After stirring for 1 hour, 2-(4-aminophenyl)ethanol [4] (156.22 g, 1.139 mol, manufactured by Oakwood) dissolved in NMP (227.86) g was added dropwise and stirred for 3 hours. After that, 2-aminoethanol (149.05 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise, and after stirring for 30 minutes, stirring was stopped. Tetrahydrofuran (THF, 1147 g), ammonium acetate (1,291 g) and ion-exchanged water (1291 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to methanol (2,869 g) and ion-exchanged water (4,303 g) for reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 150° C. for 8 hours to obtain 280.3 g of the target polymer compound [5] (hereinafter referred to as P-1).
Compound P-1 had a weight average molecular weight Mw of 6,495 and a polydispersity Mw/Mn of 3.5 as measured by GPC in terms of polystyrene. FIG. 1 shows the measurement results of the ¹ H-NMR spectrum of compound P-1.

[Synthesis Example 2] Synthesis of polymer compound [6]

P-1[5] (40.00 g) obtained in Synthesis Example 1 and 135.08 g of tetrahydrofuran (THF, manufactured by Junsei Chemical Co., Ltd.) were added to a 300 mL four-necked flask, and the mixture was purged with nitrogen and then stirred. to dissolve. Thereafter, the solution was heated until the internal temperature reached 65° C., and 0.0040 g of N-nitrosophenylhydroxyamine aluminum salt (Q-1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2-isocyanatoethyl acrylate were added. 17.89 g (AOI-VM, manufactured by Showa Denko KK) was added dropwise, and the mixture was stirred for 1 hour while maintaining the internal temperature at 65°C. After stirring for 1 hour, 135.08 g of tetrahydrofurfuryl acrylate (THFA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and THF was completely distilled off with an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as called P-1 solution)

[Synthesis Example 3] Synthesis of polymer compound [7]

In a 3,000 mL four-necked flask, 1,3-phenylenediamine [2] (47.5 g, 0.439 mol, manufactured by Amino-Chem) and 3-methoxy-N, N-dimethylpropanamide 799.2 g (KJCMPA -100, manufactured by KJ Chemicals Co., Ltd.) was added, and after purging with nitrogen, 1,3-phenylenediamine [2] was dissolved in KJCMPA-100 by stirring. Then, it is cooled to −5° C. in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (900.00 g, 0.488 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). was added while making sure that the internal temperature did not exceed 5° C., and finally washed away with KJCMPA-100 (192.6 g). After stirring for 30 minutes, the reaction solution was heated until the internal temperature reached 85°C ± 5°C, and N-ethyldiethanolamine (78.0 g, manufactured by Kanto Kagaku Co., Ltd.) was added so that the internal temperature did not exceed 90°C. I put it in while After stirring for 4 hours, 2-(4-aminophenyl)ethanol [4] (93.7 g, 0.683 mol, manufactured by Oakwood) dissolved in KJCMPA-100 (180.0 g) was added dropwise, and KJCMPA-100 ( 20.7 g), N-ethyldiethanolamine (52.0 g) was added dropwise, and the mixture was stirred for 3 hours. After that, 2-aminoethanol (29.8 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise, and after stirring for 30 minutes, stirring was stopped. Tetrahydrofuran (THF, 360 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (900.0 g) and ion-exchanged water (900.0 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to a mixture of methanol (1260 g) and ion-exchanged water (2160 g) for reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 150° C. for 8 hours to obtain 122.2 g of the objective polymer compound [7] (hereinafter referred to as P-2).
Compound P-2 had a weight-average molecular weight Mw of 3,816 and a polydispersity Mw/Mn of 2.9 as measured by GPC in terms of polystyrene. FIG. 2 shows the measurement results of the ¹ H-NMR spectrum of compound P-2.

[Synthesis Example 4] Synthesis of polymer compound [8]

P-2[7] (80.0 g) obtained in Synthesis Example 3 and THF (289.09 g) were added to a 1000 mL four-necked flask, purged with nitrogen, and dissolved by stirring. After that, the solution is heated until the internal temperature reaches 65° C., and 0.0080 g of N-nitrosophenylhydroxyamine aluminum salt (Q-1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2-isocyanatoethyl acrylate 43 are added. .90 g (AOI-VM, manufactured by Showa Denko KK) was added dropwise, and the mixture was stirred for 3 hours while maintaining the internal temperature at 65°C. After stirring for 3 hours, 289.09 g of tetrahydrofurfuryl acrylate (THFA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and THF was completely distilled off with an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as called P-2 solution).

[2] Preparation of Surface-Treated Inorganic Fine Particles Methods and apparatus for measuring physical properties carried out in Production Examples 1 to 4 below are shown below.
(1) Moisture content: determined by Karl Fischer titration.
(2) Primary particle size: The dispersion was dried on a copper mesh and observed with a transmission electron microscope to measure the particle size of 100 particles, and the average value was determined as the primary particle size.
(3) Specific gravity: Determined by floating balance method (20°C).
(4) Viscosity: Determined with an Ostwald viscometer (20°C).
(5) Particle size by dynamic light scattering method: Measured with Zetasizer Nano manufactured by Malvern.
(6) Solid content concentration: It was obtained from the remaining solid content when fired at 500°C.
(7) Bonded amount of organic silane compound: The amount of the organic silane compound bound to the modified metal oxide colloidal particles was determined by elemental analysis.
Apparatus: Series II CHNS/O Analyzer 2400 manufactured by PerkinElmer

[Production Example 1]: Production of core particles (A) and core particles (A1) Put 126.2 g of pure water in a 1-liter container, add 438 g of a 35% by mass tetraethylammonium hydroxide aqueous solution (manufactured by Seichem Japan), and metastannic acid. 17.8 g (containing 15 g in terms of SnO2, manufactured by Showa Kako Co., Ltd.), 284 g of titanium tetraisopropoxide (containing 80 g in terms of _TiO2 , manufactured by Nippon Soda Co., Ltd. A-1), and oxalic acid _dihydrate Substance 98 (contains 70 g in terms of oxalic acid, manufactured by Ube Industries, Ltd.) was added with stirring. The resulting mixed solution had a molar ratio of oxalic acid/titanium atoms of 0.78 and a molar ratio of tetraethylammonium hydroxide/titanium atoms of 1.04. 950 g of the mixed solution was held at 80° C. for 2 hours, and further reduced to 580 Torr and held for 2 hours to prepare a titanium mixed solution. The titanium mixed solution after preparation had a pH of 4.7, an electrical conductivity of 27.2 mS/cm, and a metal oxide concentration of 10.0% by mass. 950 g of the titanium mixed solution and 950 g of pure water were charged into a 3-liter glass-lined autoclave container, and hydrothermally treated at 140° C. for 5 hours. After cooling to room temperature, the hydrothermally treated solution taken out was an aqueous dispersion of pale milky white titanium oxide-containing colloidal particles. The resulting dispersion had a pH of 3.9, a conductivity of 19.7 mS/cm, a _TiO2 concentration of 4.2 wt%, a tetraethylammonium hydroxide concentration of 8.0 wt%, an oxalic acid concentration of 3.7 wt%, a dynamic Oval particles with a primary particle diameter of 4 to 10 nm were observed by light scattering method particle diameter 16 nm and transmission electron microscope observation. The obtained dispersion was dried at 110° C. and the powder was subjected to X-ray diffraction analysis to confirm that it was a rutile crystal. The obtained colloidal particles containing titanium oxide were used as core particles (A). Next, 70.8 g of zirconium oxychloride ₍ containing 21.19% by mass as ZrO2, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was diluted with 429.2 g of pure water to obtain 500 g of an aqueous zirconium oxychloride solution ( ₃ as ZrO2). 0% by mass) was separately prepared, and 1,000 g of a dispersion (aqueous dispersion sol) of the core particles (A) desalted with an ultrafiltration membrane was added thereto with stirring. Then, the mixture was heated to 95° C. for hydrolysis to obtain a water-dispersed sol of titanium oxide-containing core particles (A1) (hereinafter referred to as core particles (A1)) having a zirconium oxide thin film layer formed on the surface thereof. . The resulting water-dispersed sol had a pH of 1.2 and a total metal oxide concentration of 20% by mass, and colloidal particles having a primary particle diameter of 4 to 10 nm were observed by transmission electron microscope observation.

[Production Example 2]: Production of Coating Particles (B) 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass of _SiO2 , manufactured by Fuji Chemical Co., Ltd.) was dissolved in 1,282 g of pure water, followed by , and 20.9 g of sodium stannate NaSnO ₃ .H ₂ O (containing 55.1% by mass as SnO ₂ , manufactured by Showa Kako Co., Ltd.) were dissolved. The obtained aqueous solution is passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to obtain a water-dispersed sol of acidic silicon dioxide-stannic oxide composite colloidal particles (B1). 2,634 g (pH 2.4, containing 0.44 mass % as SnO ₂ , 0.87 mass % as SiO ₂ , SiO ₂ /SnO ₂ mass ratio 2.0). Then, 6.9 g of diisopropylamine was added to the obtained water-dispersed sol. The obtained sol was a water-dispersed sol of alkaline silicon dioxide-stannic oxide composite colloidal particles (B1) (hereinafter referred to as coating particles (B1)) and had a pH of 8.0. In the water-dispersed sol, colloidal particles having a primary particle diameter of 4 nm or less were observed with a transmission electron microscope.

[Production Example 3]: Production of modified colloidal particles (C1) 1,455 g of the water-dispersed sol of the core particles (A1) obtained in Production Example 1 was added to the water-dispersed sol of the coating particles (B1) prepared in Production Example 2. 2,634 g was added under stirring. Then, the liquid was passed through a column packed with 500 ml of an anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Corporation). Next, after heating the water-dispersed sol after passing the liquid at 95 ° C. for 3 hours, the liquid was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and tri-n-pentyl Silicon dioxide-stannic oxide stabilized with amine and concentrated by ultrafiltration membrane method to form an intermediate thin film layer composed of zirconium oxide between the core particles (A1) and the coating particles (B1) A water-dispersed sol of composite oxide-coated titanium oxide-containing colloidal particles (C1) (hereinafter referred to as modified colloidal particles (C1)) was obtained. The resulting water-dispersed sol had a total metal oxide concentration of 20 mass %, and the primary particle diameter of this sol was 4 to 10 nm as determined by transmission electron microscope observation. Then, the dispersion medium of the resulting water-dispersed sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of modified colloidal particles (C1). This methanol-dispersed sol had a total metal oxide concentration of 30% by mass, a viscosity of 1.5 mPa·s, a particle diameter of 18 nm as determined by the dynamic light scattering method, and a water content of 1.0% by mass.

[Production Example 4]: Production of surface-modified colloidal particles (D1) Polyether-modified silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 8.0 g of X-12-641) was added and heated under reflux at 70° C. for 5 hours. Next, 6.4 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) was added and heated under reflux at 70° C. for 5 hours to obtain polyether-modified silane and methacryloxy. A methanol dispersion of surface-modified colloidal particles (D1) having surfaces bound to propylsilane (hereinafter referred to as surface-modified colloidal particles (D1)) was obtained. Next, using an evaporator, methanol is distilled off while adding propylene glycol monomethyl ether at 80 Torr to replace methanol with propylene glycol monomethyl ether, and 530 g of the propylene glycol monomethyl ether dispersion of the surface-modified colloidal particles (D1) is obtained. Obtained. The resulting dispersion has a specific gravity of 1.209, a viscosity of 3.6 mPa s, a total metal oxide concentration of 30.0% by mass, a primary particle diameter of 4 to 10 nm as observed by a transmission electron microscope, and dynamic light scattering particles. The diameter was 11 nm. In the resulting surface-modified colloidal particles (D1), the polyether-modified silane bound to the surfaces of the modified colloidal particles (C1) was 4.0% by mass with respect to the total metal oxides of the modified colloidal particles (C1). , methacryloxypropylsilane bound to the particle surface was 2.5% by mass with respect to the total metal oxides of the modified colloidal particles (C1).

[Production Example 5]
310.83 g of the propylene glycol monomethyl ether dispersion (total metal oxide concentration: 30.0% by mass) of the surface-modified colloidal particles (D1) obtained in Production Example 4 and 217.73 g of acryloylmorpholine were placed in a 1 L eggplant flask. (ACMO, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and propylene glycol monomethyl ether was completely distilled off with an evaporator to obtain a 30% by mass ACMO solution (hereinafter referred to as T-1 solution).

[Production Example 6]: Production of core particles (A2) Put 255.2 g of pure water in a 1-liter container, add 438 g of a 35% by mass tetraethylammonium hydroxide aqueous solution (manufactured by Seichem Japan), 10.1 g of metastannic acid (SnO ₂ 8.6 g in terms of conversion, manufactured by Showa Kako Co., Ltd.), 325.2 g of titanium tetraisopropoxide (containing 91.4 g in terms of TiO ₂ , manufactured by Nippon Soda Co., Ltd. A-1), and oxalic acid dihydrate 75.0 g (contains 53.6 g of oxalic acid, manufactured by Ube Industries, Ltd.) was added with stirring. The resulting mixed solution had a molar ratio of oxalic acid/titanium atoms of 0.52 and a molar ratio of tetraethylammonium hydroxide/titanium atoms of 0.70. 1000 g of the mixed solution was kept at 80° C. for 2 hours, and the pressure was further reduced to 580 Torr to distill off isopropanol to prepare a titanium mixed solution. The titanium mixed solution after preparation had a pH of 5.2, an electrical conductivity of 25.2 mS/cm, and a metal oxide concentration of 10.0% by mass. 1,000 g of the titanium mixed solution and 1,000 g of pure water were put into a 3-liter glass-lined autoclave container, and hydrothermally treated at 140° C. for 5 hours. After cooling to room temperature, the hydrothermally treated solution taken out was an aqueous dispersion of pale milky white titanium oxide-containing colloidal particles. The resulting dispersion has a pH of 3.9, a conductivity of 19.2 mS/cm, a _TiO2 concentration of 5.0 wt%, a tetraethylammonium hydroxide concentration of 7.7 wt%, an oxalic acid concentration of 2.7 wt%, a dynamic Oval particles with a primary particle diameter of 4 to 10 nm were observed by light scattering method particle diameter 15 nm and transmission electron microscope observation. The obtained dispersion was dried at 110° C. and the powder was subjected to X-ray diffraction analysis to confirm that it was a rutile crystal. The obtained colloidal particles containing titanium oxide were used as core particles (A2).

[Production Example 7]: Production of modified colloidal particles (C2) To 1145 g of the dispersed sol of the coated particles (B1) obtained in Production Example 2, 2000 g of the dispersed sol containing the core particles (A2) desalted by ultrafiltration was added. It was gradually added under stirring and kept at 95° C. for 2 hours. After that, the liquid was passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), stabilized with tri-n-pentylamine, concentrated by an ultrafiltration membrane method, and silicon dioxide. - A water-dispersed sol of stannic oxide composite oxide-coated titanium oxide-containing colloidal particles (C2) (hereinafter referred to as modified colloidal particles (C2)) was obtained. The resulting water-dispersed sol had a total metal oxide concentration of 18% by mass, and a primary particle size of this sol was 4 to 10 nm when observed with a transmission electron microscope. Then, the dispersion medium of the resulting water-dispersed sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of modified colloidal particles (C2). This methanol-dispersed sol had a total metal oxide concentration of 30% by mass, a viscosity of 1.3 mPa·s, a particle diameter of 15 nm as determined by the dynamic light scattering method, and a water content of 1.2% by mass.

[Production Example 8]: Production of surface-modified colloidal particles (D2) Polyether-modified silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 5.8 g of X-12-641) was added and heated under reflux at 70° C. for 5 hours. Next, using an evaporator, methanol was distilled off while adding propylene glycol monomethyl ether at 80 Torr to replace methanol with propylene glycol monomethyl ether, and 288 g of the propylene glycol monomethyl ether dispersion of the surface-modified colloidal particles (D2) was obtained. Obtained. The resulting dispersion has a specific gravity of 1.365, a viscosity of 5.3 mPa s, a total metal oxide concentration of 40.5% by mass, a primary particle diameter of 4 to 10 nm as observed by a transmission electron microscope, and dynamic light scattering particles. The diameter was 11 nm. In the resulting surface-modified colloidal particles (D2), the polyether-modified silane bonded to the surfaces of the modified colloidal particles (C2) was 4.0% by mass with respect to the total metal oxides of the modified colloidal particles (C2). rice field.

[Production Example 9]
246.9 g of the propylene glycol monomethyl ether dispersion (total metal oxide concentration: 40.5% by mass) of the surface-modified colloidal particles (D2) obtained in Production Example 8 and 233.3 g of acryloylmorpholine were placed in a 1 L eggplant flask. (ACMO, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and propylene glycol monomethyl ether was completely distilled off with an evaporator to obtain a 30% by mass ACMO solution (hereinafter referred to as T-2 solution).

[Production Example 10]: Production of surface-modified colloidal particles (D3) Polyether-modified silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: 8.0 g of X-12-641) was added and heated under reflux at 70° C. for 5 hours. A methanol dispersion of surface-modified colloidal particles (D3) (hereinafter referred to as surface-modified colloidal particles (D3)) having surfaces bound to polyether-modified silane was obtained. Next, using an evaporator, methanol is distilled off while adding propylene glycol monomethyl ether at 80 Torr to replace methanol with propylene glycol monomethyl ether, and 530 g of the propylene glycol monomethyl ether dispersion of the surface-modified colloidal particles (D3) is obtained. Obtained. The resulting dispersion has a specific gravity of 1.212, a viscosity of 3.2 mPa s, a total metal oxide concentration of 30.3% by mass, a primary particle diameter of 4 to 10 nm as observed by a transmission electron microscope, and dynamic light scattering particles. The diameter was 10 nm. In the resulting surface-modified colloidal particles (D3), the polyether-modified silane bonded to the surfaces of the modified colloidal particles (C1) was 3.9% by mass with respect to the total metal oxides of the modified colloidal particles (C1). rice field.

[Production Example 11]
300 g of the propylene glycol monomethyl ether dispersion (total metal oxide concentration: 30.3% by mass) of the surface-modified colloidal particles (D3) obtained in Production Example 10 and 212.1 g of acryloylmorpholine (ACMO , manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and propylene glycol monomethyl ether was completely distilled off by an evaporator to obtain a 30% by mass ACMO solution (hereinafter referred to as T-3 solution).

[Production Example 12]: Production of surface-modified colloidal particles (D4) 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) , trade name: KBM-5103) was added and heated under reflux at 70°C for 5 hours to obtain a methanol dispersion of surface-modified colloidal particles (D4). The resulting dispersion has a specific gravity of 1.063, a viscosity of 1.8 mPa s, a total metal oxide concentration of 29.9% by mass, a primary particle diameter of 4 to 10 nm as observed by a transmission electron microscope, and dynamic light scattering particles. The diameter was 18 nm. In the resulting surface-modified colloidal particles (D4), the 3-acryloxypropyltrimethoxysilane bound to the surface of the modified colloidal particles (C2) was 2.0 with respect to the total metal oxides of the modified colloidal particles (C2). % by mass.

[Production Example 13]
In a 1 L eggplant flask, 100 g of the methanol dispersion of the surface-modified colloidal particles (D4) obtained in Production Example 12 (total metal oxide concentration: 29.9% by mass) and 70.0 g of acryloylmorpholine (ACMO, Tokyo Kasei Kogyo Co., Ltd.) was added, and methanol was completely distilled off by an evaporator to obtain a 30% by mass ACMO solution (hereinafter referred to as T-4 solution).

[3] Preparation of cross-linking agent-added film-forming composition and production of cured film [Example 1-1]
P-1 solution synthesized in Synthesis Example 2 (4.913 g), T-1 solution obtained in Production Example 5 (14.740 g), DN-0075 as a cross-linking agent (manufactured by Nippon Kayaku Co., Ltd.) 1 .769 g), 0.884 g of pentaerythritol tetrakis (3-mercaptobutyrate (Kalenz MT PE1, manufactured by Showa Denko KK) as a UV radical curing aid, and OXE-02 (manufactured by BASF) as a UV radical generator. 519 g, 0.442 g of Megafac R-40 (manufactured by DIC Corporation) in a 10% by mass THFA solution as a surfactant, and 3.626 g of THFA as an additional diluted monomer were added and visually confirmed to be dissolved. A solvent solution was prepared (hereinafter referred to as NP-1 solution).
This NP-1 solution was spin-coated on a 50 mm × 50 mm × 0.7 mm alkali-free glass substrate with a spin coater at 200 rpm for 5 seconds and then at 1,480 rpm for 30 seconds. After pre-drying for 3 minutes, a cured film (hereinafter referred to as NP-1 film) was obtained by irradiating light with a wavelength of 395 nm and an exposure amount of 900 mJ/cm ² with a UV-LED irradiation device.

[Example 1-2]
A solvent-free solution was prepared in the same manner as in Example 1-1, except that the inorganic fine particle solution used was changed to the T-2 solution (14.740 g) obtained in Production Example 9 (hereinafter referred to as NP-2 solution).
Using this NP-2 solution, a cured film (hereinafter referred to as NP-2 film) was obtained under the same conditions as in Example 1-1.

[Example 1-3]
A solvent-free solution was prepared (hereinafter referred to as NP-3 solution).
Using this NP-3 solution, a cured film (hereinafter referred to as NP-3 film) was obtained under the same conditions as in Example 1-1.

[Example 1-4]
The P-2 solution (3.682 g) synthesized in Synthesis Example 4, the T-4 solution (19.330 g) obtained in Production Example 13, DN-0075 as a cross-linking agent (manufactured by Nippon Kayaku Co., Ltd., 0 0.663 g), pentaerythritol tetrakis (3-mercaptobutyrate, Karenz MT PE1, manufactured by Showa Denko KK) as a UV radical curing aid, 0.663 g, and OXE-02 (manufactured by BASF) as a UV radical generator. 331 g, 0.066 g of Megafac R-40 (manufactured by DIC Corporation) in a 10% by mass THFA solution as a surfactant, and THFA (5.265 g) as an additional dilution monomer were added and dissolved visually. Then, a solvent-free solution was prepared (hereinafter referred to as NP-4 solution).
This NP-4 solution was spin-coated on a non-alkali glass substrate of 50 mm × 50 mm × 0.7 mm with a spin coater at 200 rpm for 5 seconds and 500 rpm for 30 seconds, and temporarily dried at 100 ° C. for 3 minutes using a hot plate. After that, a cured film (hereinafter referred to as NP-4 film) was obtained by irradiating with a UV-LED irradiation device at a wavelength of 395 nm and an exposure amount of 900 mJ/cm ² under nitrogen.

[Example 1-5]
A solvent-free solution was prepared in the same manner as in Example 1-4, except that the UV radical curing aid was omitted (hereinafter referred to as NP-5 solution).
Using this NP-5 solution, a cured film (hereinafter referred to as NP-5 film) was obtained under the same conditions as in Example 1-4.

[Example 1-6]
Example 1- except that no UV radical curing aid was used and the UV radical generator used was changed from OXE-02 (manufactured by BASF) 0.331 g to Omnirad 819 (manufactured by BASF) 0.331 g A solvent-free solution was prepared in the same manner as in 4 (hereinafter referred to as NP-6 solution).
Using this NP-6 solution, a cured film (hereinafter referred to as NP-6 film) was obtained under the same conditions as in Example 1-4.

For the cured film obtained above, the refractive index, film thickness, b ^* , transmittance at 400 to 800 nm, and HAZE were measured. The results are shown in Tables 1-1 and 1-2. Regarding the transmittance, the average transmittance of 400 to 800 nm was calculated and shown in Tables 1-1 and 1-2.

From these results, the cured film prepared using the solvent-free compositions obtained in Examples 1-1 to 1-6 maintains a high refractive index and high transmittance while maintaining a low HAZE. It turns out that it has the outstanding effect.

[Viscosity measurement]
[Example 2-1]
Using the NP-1 solution obtained in Example 1-1, the viscosity at 25° C. to 45° C. was measured using an EMS viscometer.

[Example 2-2]
The viscosity of the NP-2 solution obtained in Example 1-2 was measured in the same manner as in Example 2-1.

[Example 2-3]
The viscosity of the NP-3 solution obtained in Example 1-3 was measured in the same manner as in Example 2-1.

[Example 2-4]
The viscosity of the NP-4 solution obtained in Example 1-4 was measured in the same manner as in Example 2-1.

[Example 2-5]
The viscosity of the NP-5 solution obtained in Example 1-5 was measured in the same manner as in Example 2-1.

[Example 2-6]
The viscosity of the NP-6 solution obtained in Example 1-6 was measured in the same manner as in Example 2-1.

The measured viscosity at each temperature is shown in Tables 2-1 and 2-2.

From these results, it can be seen that when the temperature is raised to 35°C or higher, the viscosity is reduced to about 20 mPa·s or less, and it can be seen that application to inkjet coating and the like is sufficiently possible.

[Thick film (10 μm or more) solvent resistance (crack resistance) and transmittance, HAZE measurement]
[Example 3-1-1]
The NP-1 solution obtained in Example 1-1 was applied onto a non-alkali glass substrate of 50 mm × 50 mm × 0.7 mm with a spin coater at 200 rpm for 5 seconds and 200 rpm for 30 seconds. After temporary drying at 100 ° C. for 3 minutes, a cured film (hereinafter referred to as NP-1 film) is obtained by irradiating light with a wavelength of 395 nm and an exposure amount of 900 mJ / cm ² with a UV-LED irradiation device. rice field.
The substrate with the cured film prepared above was set in a spin coater, and 1 ml of propylene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds so as not to splash the liquid from the substrate. After that, the substrate was rotated at 1,000 rpm for 30 seconds to remove the solvent from the substrate. Finally, after drying at 120° C. for 10 seconds using a hot plate, the refractive index and film thickness were measured, the residual film ratio was calculated, and the film surface was observed with an optical microscope.
The residual film ratio was calculated by the following formula.
Remaining film rate (%) = [(film thickness after solvent exposure) ÷ (film thickness before solvent exposure)] × 100
Transmittance and HAZE were also measured before solvent exposure.

[Example 3-1-2]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 2-1, except that the solvent to be applied was changed to propylene glycol monomethyl ether acetate (PGMEA).

[Example 3-1-3]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 2-1, except that the solvent to be applied was changed to cyclopentanone (CPN).

[Example 3-2-1]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-1, except that the solution used was changed to the NP-2 solution.

[Example 3-2-2]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-2, except that the solution used was changed to the NP-2 solution.

[Example 3-2-3]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-3, except that the solution used was changed to the NP-2 solution.

[Example 3-3-1]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-1, except that the solution used was changed to the NP-3 solution.

[Example 3-3-2]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-2, except that the solution used was changed to the NP-3 solution.

[Example 3-3-3]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-1-3, except that the solution used was changed to the NP-3 solution.

The results of film thickness measurement, residual film ratio, 400 to 800 nm average transmittance and HAZE of Examples 3-1-1 to 3-1-3 are shown in Table 3, Example 3-2-1 to Example The results of 3-2-3 are shown in Table 4, the results of Examples 3-3-1 to 3-3-3 are shown in Table 5, and the results of Examples 3-1-1 to 3-1-3 Micrographs of the surface of the cured film after solvent exposure are shown in FIGS. Microscopic photographs of the surfaces of the cured films of Examples 3-3-1 to 3-3-3 after solvent exposure are shown in FIG. 8 and FIGS. 9 to 11, respectively.

[Solvent resistance (crack resistance)]
[Example 3-4-1]
The NP-4 film obtained in Example 1-4 was set on a spin coater and coated with 1 mL of propylene glycol monomethyl ether (PGME). Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds so as not to splash the liquid from the substrate. After that, the substrate was rotated at 1,000 rpm for 30 seconds to remove the solvent from the substrate. Finally, after drying at 100° C. for 10 seconds using a hot plate, the refractive index and film thickness were measured, the residual film ratio was calculated, and the film surface was observed with an optical microscope.
The residual film ratio was calculated by the following formula.
Remaining film rate (%) = [(film thickness before solvent exposure) ÷ (film thickness after solvent exposure)] × 100

[Example 3-4-2]
A cured film was prepared and a solvent resistance test was conducted in the same manner as in Example 3-4-1, except that the solvent to be applied was changed to propylene glycol monomethyl ether acetate (PGMEA).

[Example 3-4-3]
A cured film was prepared and a solvent resistance test was performed in the same manner as in Example 3-4-1, except that the solvent to be applied was changed to cyclopentanone (CPN).

[Example 3-5-1]
A solvent resistance test was conducted in the same manner as in Example 3-4-1, except that the membrane used was changed to NP-5 membrane.

[Example 3-5-2]
A solvent resistance test was conducted in the same manner as in Example 3-4-2, except that the membrane used was changed to NP-5 membrane.

[Example 3-5-3]
A solvent resistance test was conducted in the same manner as in Example 3-4-3 except that the membrane used was changed to NP-5 membrane.

[Example 3-6-1]
A solvent resistance test was conducted in the same manner as in Example 3-4-1, except that the membrane used was changed to NP-6 membrane.

[Example 3-6-2]
A solvent resistance test was conducted in the same manner as in Example 3-4-2, except that the membrane used was changed to NP-6 membrane.

[Example 3-6-3]
A solvent resistance test was conducted in the same manner as in Example 3-4-3, except that the membrane used was changed to NP-6 membrane.

Film thickness of Examples 3-4-1 to 3-4-3, Examples 3-5-1 to 3-5-3, and Examples 3-6-1 to 3-6-3 The results of measurement and residual film ratio are shown in Table 6, and the micrographs of the cured film after solvent exposure are shown in FIGS. 12 to 20, respectively.

From these results, the cured films obtained from the NP-1 to NP-6 solutions have an excellent effect of maintaining high transmittance and low HAZE while maintaining high solvent resistance even if the film thickness is thick. I understand. In addition, it can be seen that high solvent resistance is maintained even if the inorganic fine particles are not provided with crosslinked sites.

Claims

A triazine ring-containing triazine ring containing a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least part of the triazine ring terminal being blocked with an amino group having a bridging group a polymer;
a cross-linking agent;
inorganic fine particles;
including
does not contain organic solvents,
A solvent-free composition characterized by:

(In formula (1), R and R′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q is a ring structure having 3 to 30 carbon atoms; represents a valence group.* represents a bond.)
The solvent-free composition according to claim 1, wherein Q in formula (1) represents at least one selected from the group represented by formulas (2) to (13) and formulas (102) to (115). thing.

[In the formulas (2) to (13), R 1 to R 92 are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, represents a halogenated alkyl group or an alkoxy group having 1 to 10 carbon atoms,
R 93 and R 94 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
W 1 and W 2 are each independently a single bond, CR 95 R 96 (R 95 and R 96 are each independently a hydrogen atom, a C 1-10 alkyl group (provided that these may form a ring), or represents a halogenated alkyl group having 1 to 10 carbon atoms.), C═O, O, S, SO, SO 2 , or NR 97 (R 97 is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.),
X 1 and X 2 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or formula (14)

(In formula (14), R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. , or represents an alkoxy group having 1 to 10 carbon atoms,
Y 1 and Y 2 independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. ) represents a group represented by
* represents a bond. ]

(In formulas (102) to (115), R 1 and R 2 each independently represent an alkylene group having 1 to 5 carbon atoms which may have a branched structure. * represents a bond. .)
1. wherein R 1 to R 92 and R 98 to R 101 in the formulas (2) to (13) are each independently a hydrogen atom, a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms; The solvent-free composition according to .
2. The solventless composition according to claim 1, wherein the arylamino group having a cross-linking group is represented by formula (15).

(In formula (15), R 102 represents a cross-linking group. * represents a bond.)
5. The solventless composition according to claim 4, wherein the amino group having the cross-linking group is represented by formula (16).

(In formula (16), R 102 has the same meaning as above. * represents a bond.)
5. The solventless composition of Claim 4, wherein said R102 is a hydroxy-containing group or a (meth)acryloyl-containing group.
7. The solvent-free composition according to claim 6, wherein said R102 is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group or a group represented by the following formula (i).

(In formula (i), A 1 represents an alkylene group having 1 to 10 carbon atoms, and A 2 is a single bond or the following formula (j)

A3 represents an (a+1) -valent aliphatic hydrocarbon group which may be substituted with a hydroxy group , A4 represents a hydrogen atom or a methyl group, a represents 1 or 2 and * represents a bond. )
The R 102 is represented by a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and formulas (i-2) to (i-5) below. 8. The solventless composition according to claim 7, which is a group selected from the group:

(In formulas (i-2) to (i-5), * represents a bond.)
The solvent-free composition according to claim 2, wherein at least one halogen atom or halogenated alkyl group having 1 to 10 carbon atoms is contained in at least one aromatic ring in Q in formula (1).
Further, the solvent-free composition according to claim 1, wherein a portion of the triazine ring terminal is capped with an unsubstituted arylamino group.
2. The solventless composition according to claim 1, wherein said unsubstituted arylamino group is represented by formula (33).

(In formula (33), * represents a bond.)
The solvent-free composition according to claim 1, wherein Q in formula (1) is represented by formula (17).

(In formula (17), * represents a bond.)
2. The solventless composition according to claim 1, wherein Q in formula (1) is represented by formula (20).

(In formula (20), * represents a bond.)
The solventless composition according to claim 1, wherein the cross-linking agent is a polyfunctional (meth)acrylic compound.
The solvent-free composition according to claim 1, wherein the inorganic fine particles contain metal oxides, metal sulfurs or metal nitrides.
The solvent-free composition according to claim 1, further comprising a reactive diluent.
The solvent-free composition according to claim 16, wherein the reactive diluent is a compound having one radically polymerizable group.
The solventless composition according to claim 1, which is photocurable.
A film obtained from the solventless composition according to any one of claims 1 to 18.
An electronic device comprising a substrate and the film according to claim 19 formed on the substrate.
An optical member comprising a substrate and the film according to claim 19 formed on the substrate.